WO2022211121A1 - Structure stratifiée, film sec, produit durci et composant électronique - Google Patents

Structure stratifiée, film sec, produit durci et composant électronique Download PDF

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Publication number
WO2022211121A1
WO2022211121A1 PCT/JP2022/016968 JP2022016968W WO2022211121A1 WO 2022211121 A1 WO2022211121 A1 WO 2022211121A1 JP 2022016968 W JP2022016968 W JP 2022016968W WO 2022211121 A1 WO2022211121 A1 WO 2022211121A1
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WO
WIPO (PCT)
Prior art keywords
resin
resin layer
resin composition
laminated structure
carboxyl group
Prior art date
Application number
PCT/JP2022/016968
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English (en)
Japanese (ja)
Inventor
ハヌル チャ
大地 岡本
英和 宮部
Original Assignee
太陽インキ製造株式会社
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
Application filed by 太陽インキ製造株式会社 filed Critical 太陽インキ製造株式会社
Priority to CN202280025323.9A priority Critical patent/CN117120929A/zh
Priority to JP2023511759A priority patent/JPWO2022211121A1/ja
Priority to KR1020237035328A priority patent/KR20230165789A/ko
Publication of WO2022211121A1 publication Critical patent/WO2022211121A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • 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
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • 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
    • G03F7/095—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having more than one photosensitive layer
    • 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
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings
    • H05K3/285—Permanent coating compositions
    • H05K3/287—Photosensitive compositions

Definitions

  • the present invention relates to laminated structures, dry films, cured products suitable for use in semiconductor packages and the like, and electronic components using these.
  • B-HAST Biased HAST
  • crack resistance in thermal cycles is one of the long-term reliability tests. I have an exam.
  • a photocurable / thermosetting resin composition excellent in B-HAST resistance a compound (a) having two or more phenolic hydroxyl groups in one molecule and an alkylene oxide (b) or a cyclocarbonate compound (c)
  • a resin composition containing Patent Document 1
  • Cited Document 1 contains a carboxyl group-containing photosensitive resin having a rigid skeleton, it is excellent in B-HAST resistance. was not always sufficient.
  • an object of the present invention is to provide a laminated structure, a dry film, a cured product, and an electronic component that are not only capable of achieving high levels of the contradictory properties of B-HAST resistance and crack resistance, but also have excellent photopatternability. That's what it is.
  • the present inventors have made intensive studies to solve the above problems, and by forming a laminate of two layers with different compositions, it is possible to achieve both B-HAST resistance and crack resistance, which are contradictory properties, at a high level. It was confirmed. However, in a laminated structure in which a layer suitable for B-HAST resistance and a layer suitable for crack resistance are simply laminated, since it is difficult to control the sensitivity of each layer, it is difficult to obtain good photopatternability. It has been found. In recent years, in the use of semiconductor packages, excellent photopatternability that enables the opening diameter of solder resist openings (SRO) to be 50 ⁇ m or less is being sought.
  • SRO solder resist openings
  • the present invention was completed as a result of continuing research and development.
  • the laminated structure of the present invention comprises two resin layers in which a resin layer (A) made of the resin composition (a) and a resin layer (B) made of the resin composition (b) are laminated.
  • a laminated structure having The resin composition (b) of the resin layer (B) comprises an alkali-soluble resin, a photobase generator or a photopolymerization initiator and a photobase generator having the function of a photopolymerization initiator, a thermosetting resin, including
  • the resin composition (a) of the resin layer (A) contains a carboxyl group-containing resin and a thermosetting resin and does not substantially contain a photopolymerization initiator,
  • a PEB POST EXPOSURE BAKE
  • the definitions of glossiness sensitivity and residual sensitivity are as follows. After exposing the two resin layers from the resin layer (B) side through a step tablet and performing the PEB process, the coating thickness of the two resin layers before development of the formed pattern was 100. %, the gloss sensitivity is defined as the largest value of the number of steps at which 95% or more of the coating thickness remains after the PEB process after the exposure and the coating thickness before the development. is defined as 100%, the maximum value of the number of steps at which the coating thickness becomes 5% or less after the development was defined as the residual sensitivity.
  • the coating thickness of the formed pattern conforms to JIS K 5600-1-7: 2014, and is obtained as the measured value obtained as the thickness of the entire coating thickness and the thickness of the substrate. It was measured as a difference from the measured value.
  • the measurement method is a mechanical measurement method, using a thickness gauge (DIGIMICRO MF-501, manufactured by Nikon Corporation), exposing the two resin layers from the resin layer (B) side through a step tablet, After performing the PEB process at 90 ° C.
  • the coating film thickness of the formed pattern before development, and the coating film of the remaining coating film formed after the PEB process after the exposure and after the development The thickness is measured, and when the coating film before development is taken as 100%, the largest value of the number of steps at which 95% or more of the coating film remains after the development is taken as the gloss sensitivity, and the coating film before development is defined as the gloss sensitivity. When the thickness is taken as 100%, the maximum value of the number of steps at which the coating thickness becomes 5% or less after the development is defined as the residual sensitivity.
  • the thickness of the resin layer (B) is 2 ⁇ m or more and not more than half the thickness of the resin layer (A), and the thickness of the resin layer (A) is 10 to 10 ⁇ m. It is preferably 80 ⁇ m, more preferably 20-60 ⁇ m.
  • the dry film of the present invention is in contact with the laminated structure of the present invention and at least one surface of the surface of the resin layer (B) and the surface of the resin layer (A) of the laminated structure. and a film provided.
  • the cured product of the present invention is characterized by being obtained by curing the laminated structure of the present invention or the laminated structure of the dry film of the present invention.
  • the electronic component of the present invention is characterized by having the cured product of the present invention.
  • the laminate structure of the present invention is a laminate having two resin layers in which a resin layer (A) made of the resin composition (a) and a resin layer (B) made of the resin composition (b) are laminated.
  • the resin composition (b) of the resin layer (B) comprises an alkali-soluble resin, a photobase generator or a photopolymerization initiator and a photobase generator having the function of a photopolymerization initiator, a thermosetting resin, including
  • the resin composition (a) of the resin layer (A) contains a carboxyl group-containing resin and a thermosetting resin and does not substantially contain a photopolymerization initiator, After exposing the two resin layers from the resin layer (B) side through a step tablet and performing the PEB process, the coating thickness of the formed pattern and the PEB process were performed after the exposure.
  • the difference between the glossiness sensitivity and the remaining sensitivity obtained by measuring the coating thickness of the pattern formed by development is 20 steps or less, more preferably 14 steps or less.
  • the laminated structure When the laminated structure is formed on a substrate, the layer in contact with the substrate is the resin layer (A), and the surface of the resin layer (A) opposite to the surface in contact with the substrate is the resin layer (B). That is, the laminated structure has a structure in which the resin layer (A) and the resin layer (B) are laminated in this order on the substrate.
  • the base material include a printed wiring board, a flexible printed wiring board, and the like on which a circuit is formed in advance using copper or the like.
  • the resin layer (B) is a resin composition (b) containing an alkali-soluble resin, a photobase generator or a photopolymerization initiator and a photobase generator having the function of a photopolymerization initiator, and a thermosetting resin.
  • the resin composition (b) of the resin layer (B) containing these components has photosensitivity due to the reaction of the photopolymerization initiator with the alkali-soluble resin by light irradiation, and the photobase of the polymerization initiator by heating. It is a photosensitive thermosetting resin composition that can be thermally cured with its function as a generator serving as a catalyst.
  • the resin layer (A) is composed of a resin composition (a) containing a carboxyl group-containing resin and a thermosetting resin and substantially free of a photopolymerization initiator.
  • substantially free of photopolymerization initiator means that the amount of photopolymerization initiator is less than 0.5 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin contained in the resin composition (a). Since the resin composition (a) of the resin layer (A) containing these components does not contain a photopolymerization initiator, it does not have photosensitivity in a single layer, but it is laminated in contact with the resin layer (B).
  • the resin layer (A) Since active species such as radicals generated from the photopolymerization initiator contained in the resin layer (B) diffuse into the resin layer (A), the resin layer (A) also has photosensitivity. ing. Moreover, it can be thermoset by heating. Therefore, in the laminated structure, a predetermined pattern can be collectively formed on the resin layer (B) and the resin layer (A) by development. In particular, when the PEB process is performed after the exposure, the effect of batch formation of patterns is remarkable due to thermal diffusion at that time.
  • a resin layer (A) consists of a resin composition (a). It is desirable that the resin composition (a) of the resin layer (A) not only functions as an adhesive layer with the base material, but also has properties capable of coping with formation of various circuit patterns. Therefore, the resin composition (a) of the resin layer (A) is added with a resin having a carboxyl group, especially a carboxyl group-containing resin, and a thermosetting component using a base generated from a base generator as a catalyst by heating after exposure. It is preferably a photosensitive thermosetting resin composition that can be developed by reacting and removing the unexposed portions with an alkaline solution.
  • carboxyl group-containing resin contained in the resin composition (a) of the resin layer (A) include the following compounds.
  • Carboxyl group-containing resins obtained by copolymerizing unsaturated carboxylic acids such as (meth)acrylic acid and unsaturated group-containing compounds such as styrene, ⁇ -methylstyrene, lower alkyl (meth)acrylates, and isobutylene.
  • Diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates and aromatic diisocyanates; Carboxyl group-containing urethane resins obtained by polyaddition reaction of diol compounds such as polyols, polyester-based polyols, polyolefin-based polyols, acrylic polyols, bisphenol A-based alkylene oxide adduct diols, and compounds having phenolic hydroxyl groups and alcoholic hydroxyl groups.
  • diol compounds such as polyols, polyester-based polyols, polyolefin-based polyols, acrylic polyols, bisphenol A-based alkylene oxide adduct diols, and compounds having phenolic hydroxyl groups and alcoholic hydroxyl groups.
  • Diisocyanate compounds such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, and aromatic diisocyanates, polycarbonate-based polyols, polyether-based polyols, polyester-based polyols, polyolefin-based polyols, acrylic polyols, and bisphenol A-based A terminal carboxyl group-containing urethane resin obtained by reacting an acid anhydride with the terminal of a urethane resin obtained by a polyaddition reaction of a diol compound such as an alkylene oxide adduct diol, a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group.
  • a diol compound such as an alkylene oxide adduct diol, a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group.
  • Diisocyanate and bifunctional epoxy resin such as bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bixylenol type epoxy resin, biphenol type epoxy resin ( A carboxyl group-containing urethane resin produced by a polyaddition reaction of a meth)acrylate or its partial acid anhydride modified product, a carboxyl group-containing dialcohol compound and a diol compound.
  • a carboxyl group-containing polyester resin obtained by reacting a polyfunctional oxetane compound with a dicarboxylic acid and adding a dibasic acid anhydride to the resulting primary hydroxyl group.
  • reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with an alkylene oxide such as ethylene oxide or propylene oxide and reacting an unsaturated group-containing monocarboxylic acid to obtain a reaction product
  • alkylene oxide such as ethylene oxide or propylene oxide
  • unsaturated group-containing monocarboxylic acid to obtain a reaction product
  • a carboxyl group-containing resin obtained by reacting a polybasic acid anhydride with a substance.
  • (11) Obtained by reacting a reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with a cyclic carbonate compound such as ethylene carbonate or propylene carbonate with a monocarboxylic acid containing an unsaturated group.
  • a carboxyl group-containing resin obtained by reacting a reaction product with a polybasic acid anhydride.
  • an epoxy resin having a plurality of epoxy groups in one molecule a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule, such as p-hydroxyphenethyl alcohol;
  • a carboxyl group-containing resin having at least one of an amide structure and an imide structure A maleimide or maleimide derivative such as N-phenylmaleimide or N-benzylmaleimide, an unsaturated carboxylic acid such as (meth)acrylic acid, and an unsaturated group-containing compound having a hydroxyl group such as hydroxyalkyl (meth)acrylate , styrene, ⁇ -methylstyrene, ⁇ -chlorostyrene, a carboxyl group-containing copolymer resin having an unsaturated group-containing compound having an aromatic ring such as vinyltoluene as a monomer, glycidyl (meth) acrylate, ⁇ -methyl
  • the carboxyl group-containing resin contained in the resin composition (a) of the resin layer (A) can be used without being limited to those listed above. may be used.
  • the above carboxyl group-containing resins (10) which is an ethylene oxide (EO)/propylene oxide (PO) modified resin starting from a phenolic resin and (11) which is an ethylene carbonate/propylene carbonate modified resin starting from a phenolic resin have photosensitive groups. and the developing unit having a carboxyl group are independent of each other, so that even after the photosensitive groups are crosslinked by exposure, a good contrast between the exposed and unexposed areas can be obtained without affecting the developability of the developing unit having a carboxyl group. This is preferable because it facilitates sensitivity adjustment.
  • the carboxyl group-containing resins (10) and (11) may be used in combination with the carboxyl group-containing urethane resins (2) to (6).
  • the amount of the carboxyl group-containing resin contained in the resin composition (a) of the resin layer (A) is 10 to 70% by mass based on the total solid content of the resin composition (a). By making it 10% by mass or more, the strength of the coating film can be improved. Moreover, by making it 70% by mass or less, the viscosity becomes appropriate and the workability improves.
  • the resins (10) and (11) are preferably 30 to 100% by mass, more preferably 70 to 100% by mass, in the carboxyl group-containing resin of the resin layer (A). 100% by mass. Within this range, it is possible to narrow the difference between glossiness sensitivity and residual sensitivity to 20 steps or less at a constant exposure amount.
  • the resin composition (a) of the resin layer (A) does not substantially contain a photopolymerization initiator, from the viewpoint of adjusting the gloss sensitivity and residual sensitivity of the resin laminate structure.
  • substantially free of photopolymerization initiator means that the amount of photopolymerization initiator is less than 0.5 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin contained in the resin composition (a). This is because the resin composition (b) of the resin layer (B) functions as a photopolymerization initiator in order to collectively form a pattern in the laminated structure of the resin layer (B) and the resin layer (A) by development. It is sufficient to cure the resin laminate because it contains the photobase generator having the If the resin composition (a) of the resin layer (A) contains a photopolymerization initiator, the residual sensitivity tends to increase, adversely affecting fine patterning.
  • thermosetting resin contained in the resin composition (a) of the resin layer (A) is a resin having a functional group capable of thermal curing reaction.
  • Thermosetting resins are not particularly limited, and include epoxy resins, oxetane compounds, compounds having two or more thioether groups in the molecule, namely amino resins such as episulfide resins, melamine resins, benzoguanamine resins, melamine derivatives, and benzoguanamine derivatives. , blocked isocyanate compounds, cyclocarbonate compounds, bismaleimides, carbodiimides and the like can be used, and these may be used in combination.
  • the epoxy resin is a resin having an epoxy group, and any conventionally known one can be used, including a bifunctional epoxy resin having two epoxy groups in the molecule and a polyfunctional epoxy resin having many epoxy groups in the molecule. etc. In addition, a hydrogenated bifunctional epoxy resin may be used.
  • epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, brominated bisphenol A type epoxy resin, bisphenol S type epoxy resin, phenol novolak type epoxy resin, and cresol novolak type epoxy resin.
  • Epoxy resins bisphenol A novolak type epoxy resins, biphenyl type epoxy resins, naphthol type epoxy resins, naphthalene type epoxy resins, dicyclopentadiene type epoxy resins, triphenylmethane type epoxy resins, alicyclic epoxy resins, aliphatic chain Epoxy resins, phosphorus-containing epoxy resins, anthracene-type epoxy resins, norbornene-type epoxy resins, adamantane-type epoxy resins, fluorene-type epoxy resins, aminophenol-type epoxy resins, aminocresol-type epoxy resins, alkylphenol-type epoxy resins, and the like are used. These epoxy resins can be used singly or in combination of two or more.
  • the epoxy resin may be solid epoxy resin, semi-solid epoxy resin, or liquid epoxy resin.
  • solid epoxy resin refers to an epoxy resin that is solid at 40°C
  • semi-solid epoxy resin refers to an epoxy resin that is solid at 20°C and liquid at 40°C
  • a liquid epoxy resin means an epoxy resin that is liquid at 20°C.
  • EPICLON HP-4700 naphthalene type epoxy resin
  • EXA4700 tetrafunctional naphthalene type epoxy resin
  • NC-7000 polyfunctional solid epoxy resin containing naphthalene skeleton
  • EPPN-502H trisphenol epoxy resin
  • Epoxidized products of condensation products of phenols and aromatic aldehydes having phenolic hydroxyl groups (trisphenol-type epoxy resins); Dicyclopentadiene aralkyl type epoxy resin such as EPICLON HP-7200H (dicyclopentadiene skeleton-containing polyfunctional solid epoxy resin) manufactured by DIC; Biphenyl such as Nippon Kayaku NC-3000H (biphenyl skeleton-containing polyfunctional solid epoxy resin) Aralkyl-type epoxy resins; biphenyl/phenol novolac-type epoxy resins such as Nippon Kayaku NC-3000L; DIC EPICLON N660, EPICLON N690, Nippon Kayaku EOCN-104S and other novolac-type epoxy resins; biphenyl type epoxy resins such as YX-4000 manufactured by Nittetsu Chemical &Materials; phosphorus-containing epoxy resins such as TX0712 manufactured by Nippon Steel Chemical &Materials;
  • Semi-solid epoxy resins include EPICLON 860, EPICLON 900-IM, EPICLON EXA-4816, EPICLON EXA-4822 manufactured by DIC, Epotato YD-134 manufactured by Nippon Steel Chemical & Materials, jER834 and jER872 manufactured by Mitsubishi Chemical, and Sumitomo Chemical.
  • bisphenol A type epoxy resins such as ELA-134 manufactured by DIC Corporation; naphthalene type epoxy resins such as EPICLON HP-4032 manufactured by DIC Corporation; and phenol novolac type epoxy resins such as EPICLON N-740 manufactured by DIC Corporation.
  • Liquid epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol E type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, glycidylamine type epoxy resin, aminophenol type epoxy resin. , and alicyclic epoxy resins.
  • the oxetane compounds include bis[(3-methyl-3-oxetanylmethoxy)methyl]ether, bis[(3-ethyl-3-oxetanylmethoxy)methyl]ether, 1,4-bis[(3-methyl -3-oxetanylmethoxy)methyl]benzene, 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene, (3-methyl-3-oxetanyl)methyl acrylate, (3-ethyl-3-oxetanyl )
  • polyfunctional oxetanes such as methyl acrylate, (3-methyl-3-oxetanyl)methyl methacrylate, (3-ethyl-3-oxetanyl)methyl methacrylate and their oligomers or copolymers, oxetane alcohols and novolak resins, Examples include poly(p-hydroxystyrene), cardo-type bisphenol
  • the episulfide resin examples include bisphenol A type episulfide resin.
  • an episulfide resin or the like obtained by replacing the oxygen atom of the epoxy group of the epoxy resin with a sulfur atom by using a similar synthesis method can also be used.
  • thermosetting resins it is preferable to use epoxy resin. Further, at least one of solid epoxy resins and semi-solid epoxy resins is preferable, since a cured product having a high glass transition temperature (Tg) and excellent crack resistance can be obtained.
  • epoxy resin aromatic epoxy resins are preferable from the viewpoint of desirable physical properties of the cured product, and among them, naphthalene-type epoxy resins and biphenyl-type epoxy resins are more preferable.
  • the aromatic epoxy resin means an epoxy resin having an aromatic ring skeleton in its molecule.
  • the molecular weight of the thermosetting resin contained in the resin composition (a) of the resin layer (A) is preferably a weight average molecular weight of 100 to 2,000 in order to adjust the developability and properties of the cured coating film.
  • a component with a low molecular weight that is, a weight-average molecular weight (Mw) of 100 to 1,000
  • Mw weight-average molecular weight
  • the residual sensitivity step number can be increased.
  • an epoxy resin having a weight-average molecular weight of 1,000 or less is used to prevent the step number of remaining sensitivity from becoming too large.
  • thermosetting resin can be used singly or in combination of two or more.
  • the mixing ratio of the thermosetting resin is preferably 10 to 50% by mass, more preferably 15 to 45% by mass, based on the total amount of the resin composition (a) in terms of solid content, and 19 to It is more preferably 40% by mass.
  • the resin having a carboxyl group and the thermosetting component are subjected to an addition reaction by heating after exposure using the base generated from the base generator as a catalyst. It is a photosensitive thermosetting resin composition that can be developed by removing a portion with an alkaline solution. This eliminates the need to add a (meth)acrylate monomer, which is necessary in a photosensitive resin composition utilizing a polymerization reaction by radicals generated from a conventional photoradical polymerization initiator.
  • a (meth)acrylate monomer may be blended into the resin composition of the resin layer (A) mainly to adjust the sensitivity of the resin layer (A). For example, about 10 to 100 parts by mass of the (meth)acrylate monomer can be blended with 100 parts by mass of the carboxyl group-containing resin of the resin layer (A).
  • a resin layer (B) consists of a resin composition (b).
  • the resin layer (B) mainly functions as a protective layer for the substrate.
  • the resin composition (b) of the resin layer (B) is capable of radical polymerization by light due to the photopolymerization initiator, and the alkali-soluble resin and the thermosetting component are exposed to light using the base generated from the base generator as a catalyst. It is a photosensitive thermosetting resin composition that can be developed by causing an addition reaction by subsequent heating and removing unexposed portions with an alkaline solution.
  • Examples of the alkali-soluble resin contained in the resin composition (b) of the resin layer (B) include a compound having a phenolic hydroxyl group, a compound having a carboxyl group, and a compound having a phenolic hydroxyl group and a carboxyl group. are used.
  • carboxyl group-containing resins or carboxyl group-containing photosensitive resins which contain a compound having a carboxyl group and are conventionally used as solder resist compositions, can be mentioned.
  • the carboxyl group-containing resin or the carboxyl group-containing photosensitive resin and the compound having an ethylenically unsaturated bond known and commonly used compounds are used.
  • an alkali-soluble resin having an imide ring which is superior in properties such as bending resistance and heat resistance, can be preferably used.
  • the molecular weight of the carboxyl group-containing resin contained in the resin composition (b) of the resin layer (B) is preferably a weight average molecular weight of 1,000 to 10,000 in order to adjust fine patterning properties and surface curability. Within this range, when the gloss sensitivity is controlled by the molecular weight of the carboxyl group-containing resin component, the use of a carboxyl group-containing resin having a low molecular weight, that is, 1,000 to 5,000 reduces the step number of gloss sensitivity.
  • the number of steps of gloss sensitivity can be increased.
  • the alkali-soluble resin having an imide ring which will be described later, has a carboxyl group
  • the gloss sensitivity can be similarly adjusted within the weight-average molecular weight range described above.
  • the alkali-soluble resin having an imide ring has one or more alkali-soluble groups selected from phenolic hydroxyl groups and carboxyl groups, and an imide ring.
  • a well-known and commonly used technique can be used for introducing an imide ring into this alkali-soluble resin. Examples thereof include resins obtained by reacting a carboxylic anhydride component with an amine component and/or an isocyanate component. The imidization may be carried out by thermal imidization or by chemical imidization, or these may be used in combination.
  • examples of the carboxylic acid anhydride component include tetracarboxylic acid anhydrides and tricarboxylic acid anhydrides, but are not limited to these acid anhydrides. Any compound having a physical group and a carboxyl group can be used, including derivatives thereof. Also, these carboxylic acid anhydride components may be used alone or in combination.
  • diamines such as aliphatic diamines and aromatic diamines, polyvalent amines such as aliphatic polyetheramines, diamines having a carboxylic acid, diamines having a phenolic hydroxyl group, and the like can be used. is not limited to Also, these amine components may be used alone or in combination.
  • diisocyanates such as aromatic diisocyanates and their isomers and polymers, aliphatic diisocyanates, alicyclic diisocyanates and their isomers, and other general-purpose diisocyanates can be used. It is not limited. Also, these isocyanate components may be used alone or in combination.
  • the alkali-soluble resin having an imide ring as explained above may have an amide bond.
  • This may be a polyamide-imide obtained by reacting an imidized product having a carboxyl group with an isocyanate and a carboxylic acid anhydride, or may be obtained by other reactions. It may also have other bonds consisting of addition and condensation.
  • a known and commonly used organic solvent can be used.
  • an organic solvent there is no problem as long as it does not react with the carboxylic acid anhydrides, amines, and isocyanates that are raw materials and dissolves these raw materials, and its structure is not particularly limited.
  • aprotic solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethylsulfoxide, and ⁇ -butyrolactone are preferred because of their high solubility of raw materials.
  • Alkali-soluble resins having at least one alkali-soluble group and an imide ring selected from phenolic hydroxyl groups and carboxyl groups as described above correspond to photolithography processes, and in order to adjust gloss sensitivity and residual sensitivity, Its acid value is preferably 20-200 mgKOH/g, more preferably 60-150 mgKOH/g.
  • the acid value is 20 mgKOH/g or more, the solubility in alkali increases, the developability becomes good, and the degree of crosslinking with the thermosetting component after light irradiation increases, so that sufficient development contrast is obtained. be able to.
  • the acid value is 200 mgKOH/g or less, so-called heat fogging can be suppressed particularly in the PEB process after light irradiation, which will be described later, and the process margin is increased.
  • the molecular weight of this alkali-soluble resin is preferably a mass average molecular weight of 1,000 to 100,000, more preferably 2,000 to 50,000, in order to adjust the developability and properties of the cured coating film.
  • this molecular weight is 1,000 or more, sufficient development resistance and cured physical properties can be obtained after exposure and PEB. Further, when the molecular weight is 100,000 or less, the alkali solubility is increased and the developability is improved.
  • photopolymerization initiator used in the resin composition (b) of the resin layer (B)
  • known and commonly used photopolymerization initiators can be used, such as benzoin compounds, acylphosphine oxide compounds, acetophenone compounds, ⁇ -aminoacetophenone compounds, oxime ester compounds, thioxanthone compounds, and the like.
  • the resin composition (b) of the resin layer (B) can be radically polymerized by light by containing a photopolymerization initiator.
  • a photopolymerization initiator that also functions as a photobase generator is suitable.
  • a photopolymerization initiator and a photobase generator may be used together.
  • the amount of the photopolymerization initiator compounded is preferably 0.5 to 30 parts by mass with respect to 100 parts by mass of the alkali-soluble resin. When the amount is 0.5 parts by mass or more, the surface curability is improved, and when the amount is 30 parts by mass or less, halation is less likely to occur and good resolution is obtained. More preferably, it is 1.0 to 20 parts by mass.
  • the photobase generator which also functions as a photopolymerization initiator, undergoes a polymerization reaction of the heat-reactive compound described below by changing its molecular structure or by cleaving the molecule upon irradiation with light such as ultraviolet light or visible light.
  • photobase generators also functioning as photopolymerization initiators include ⁇ -aminoacetophenone compounds, oxime ester compounds, acyloxyimino groups, N-formylated aromatic amino groups, N-acylated aromatic and compounds having substituents such as group amino groups, nitrobenzylcarbamate groups, alkoxybenzylcarbamate groups, and the like.
  • oxime ester compounds and ⁇ -aminoacetophenone compounds are preferred, and oxime ester compounds are more preferred.
  • ⁇ -aminoacetophenone compounds those having two or more nitrogen atoms are particularly preferred.
  • Any ⁇ -aminoacetophenone compound may be used as long as it has a benzoin ether bond in the molecule and undergoes intramolecular cleavage when exposed to light to generate a basic substance (amine) that acts as a curing catalyst.
  • any compound can be used as the oxime ester compound as long as it is a compound that generates a basic substance upon irradiation with light.
  • the amount of the photobase generator compounded in the resin composition is preferably 1.0 to 40 parts by mass, more preferably 1.0 to 20 parts by mass, per 100 parts by mass of the alkali-soluble resin.
  • the amount is 1.0 parts by mass or more, a good contrast of the development resistance between the light-irradiated area and the non-irradiated area can be obtained.
  • it is 40 parts by mass or less, the properties of the cured product are improved.
  • thermosetting resin The thermosetting resin (b) of the resin layer (B) is an epoxy resin, an oxetane compound, or a compound having two or more thioether groups in the molecule, similar to the thermosetting resin of the resin layer (A) described above. ie, episulfide resins, melamine resins, benzoguanamine resins, melamine derivatives, amino resins such as benzoguanamine derivatives, blocked isocyanate compounds, cyclocarbonate compounds, bismaleimides, carbodiimides, etc., may be used in combination.
  • thermosetting resin (b) of the resin layer (B) may be the same thermosetting resin as the thermosetting resin of the resin layer (A), or may be a different thermosetting resin. Moreover, a thermosetting resin can be used individually by 1 type or in combination of 2 or more types.
  • the blending ratio of the thermosetting resin is preferably 10 to 50% by mass, more preferably 15 to 45% by mass, more preferably 20 to 40% by mass, based on the total amount of the composition in terms of solid content. is more preferred.
  • the resin composition used in the resin layer (A) and the resin layer (B) as described above may optionally contain the following components.
  • coloring agent A coloring agent can be added for the purpose of adjusting sensitivity.
  • known and commonly used colorants such as red, blue, green, yellow, white, and black can be blended, and any of pigments, dyes, and pigments can be used.
  • antioxidants for the purpose of adjusting the sensitivity and improving the properties of the effect paint, known and commonly used additives such as antioxidants, ultraviolet absorbers, finely divided silica, hydrotalcite and silane coupling agents can be added.
  • the thickness of the resin layer (B) is 2 ⁇ m or more and not more than half the thickness of the resin layer (A), and the thickness of the resin layer (A) is preferably 10 to 80 ⁇ m, preferably 20 to 60 ⁇ m is more preferred.
  • the laminated structure may be formed by forming the resin composition of the resin layer (A) and the resin composition of the resin layer (B) into a dry film on a base material such as a wiring board, or by forming a liquid one.
  • the layers may be coated and formed sequentially.
  • When used as a liquid it may be one-liquid or two-liquid or more, but from the viewpoint of storage stability, it is preferably two-liquid or more.
  • the dry film of the present invention is obtained by coating the resin composition (a) of the resin layer (A) and the resin composition (b) of the resin layer (B) on the first film, followed by drying. It has a resin layer that is When forming the dry film, first, the resin composition (a) of the resin layer (A) and the resin composition (b) of the resin layer (B) were diluted with the above organic solvent to adjust the viscosity to an appropriate value. Then, it is coated on a carrier film to a uniform thickness by a comma coater, blade coater, lip coater, rod coater, squeeze coater, reverse coater, transfer roll coater, gravure coater, spray coater, or the like.
  • the applied composition is usually dried at a temperature of 40 to 130° C. for 1 to 30 minutes to form a resin layer.
  • the thickness of the coating is not particularly limited, but is generally selected appropriately within the range of 5 to 150 ⁇ m, preferably 15 to 60 ⁇ m, in terms of thickness after drying.
  • a plastic film is used as the first film, and for example, a polyester film such as polyethylene terephthalate (PET), a polyimide film, a polyamideimide film, a polypropylene film, a polystyrene film, or the like can be used.
  • the thickness of the first film is not particularly limited, but is generally selected appropriately within the range of 10 to 150 ⁇ m. More preferably, it is in the range of 15 to 130 ⁇ m.
  • the adhesion of dust to the surface of the film was confirmed.
  • a peelable cover film on the surface of the membrane.
  • the peelable second film for example, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, surface-treated paper, or the like can be used.
  • any film may be used as long as it has an adhesive strength smaller than that between the resin layer and the first film when the cover film is peeled off.
  • the resin composition (b) of the resin layer (B) and the resin composition (a) of the resin layer (A) are coated on the second film and dried to obtain a laminated individual structure. may be formed and the first film may be laminated on the surface thereof. That is, in the production of the dry film in the present invention, the first film and the second Either of the two films may be used.
  • the resin composition of the resin layer (A) and the resin composition of the resin layer (B) are, for example, adjusted to a viscosity suitable for the coating method using the above organic solvent, and then coated on the substrate by a dip coating method, a flow After applying by a method such as coating method, roll coating method, bar coating method, screen printing method, curtain coating method, etc., the organic solvent contained in the composition is volatilized and dried (temporary drying) at a temperature of 60 to 100 ° C. , a tack-free resin layer can be formed.
  • the layer of the composition of the present invention is placed on the substrate by a laminator or the like so as to be in contact with the substrate.
  • a resin layer can be formed by peeling off the carrier film after laminating.
  • the substrate examples include printed wiring boards and flexible printed wiring boards on which circuits are formed in advance using copper or the like, paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth/non-woven cloth epoxy, glass cloth/paper epoxy. , Synthetic fiber epoxy, fluororesin, polyethylene, polyphenylene ether, polyphenylene oxide, cyanate, and other materials such as copper-clad laminates for high-frequency circuits, and copper-clad laminates of all grades (FR-4, etc.) Plates, metal substrates, polyimide films, PET films, polyethylene naphthalate (PEN) films, glass substrates, ceramic substrates, wafer plates and the like can also be used.
  • PEN polyethylene naphthalate
  • Volatilization drying performed after applying the resin composition to the substrate or the first film of the dry film can be performed by a hot air circulation drying oven, an IR oven, a hot plate, a convection oven, etc. and a method in which the hot air in the dryer is brought into contact with the counter current, and a method in which the support is blown from a nozzle). Further, the heating performed in the PEB process and the post-curing process, which will be described later, can be performed using the hot air circulating drying furnace or the like.
  • a dry film is formed on a base material for electronic parts, such as a printed wiring board, by peeling off the first film, and is cured by exposure and alkali development. After alkali development, post-curing is performed as necessary. Without using a dry film, the resin composition (a) of the resin layer (A) and the resin composition (b) of the resin layer (B) are coated and formed on the substrate, and then the cured product is obtained by exposure and alkali development. be done. After alkali development, post-curing is performed as necessary.
  • the photobase generator contained in the resin composition (b) of the resin layer (B) is activated in a negative pattern by irradiation with active energy rays to cure the exposed portion.
  • a photopolymerization initiator or photobase generator functioning as a photobase generator is activated in a negative pattern to generate a base.
  • the exposure machine used in this process includes a direct drawing machine, an exposure machine equipped with a metal halide lamp, a light irradiation machine equipped with a (ultra) high pressure mercury lamp, a light irradiation machine equipped with a mercury short arc lamp, or a (ultra)
  • a direct drawing apparatus using an ultraviolet lamp such as a high-pressure mercury lamp can be used.
  • a mask for patternwise exposure is a negative mask.
  • active energy rays used for exposure laser light or scattered light having a maximum wavelength in the range of 350 to 450 nm is preferably used. By setting the maximum wavelength within this range, the photobase generator can be efficiently activated.
  • the amount of exposure differs depending on the film thickness, etc., it is usually 100 to 1500 mJ/cm 2 .
  • the resin composition (a) of the laminated resin layer (A) and the resin composition (b) of the resin layer (B) are exposed (light irradiation) to form an exposed portion (light irradiated portion). hardens.
  • the light-irradiated portion is cured by activating the photobase generator contained in the resin layer by light irradiation in a negative pattern.
  • the photobase generator is destabilized by the base generated in the light irradiation portion, and the base chemically proliferates, so that the deep portion of the resin layer can be fully cured.
  • an exposure device used for light irradiation any device that irradiates ultraviolet rays in the range of 350 to 450 nm may be used.
  • the exposed portion is cured by heating the resin layer after exposure (light irradiation).
  • the base generated in the light irradiation step can sufficiently cure deep portions of the resin layer.
  • the heating temperature is, for example, 80-140.degree.
  • the heating time is, for example, 2 to 140 minutes.
  • Curing of the resin composition in the present invention is, for example, a ring-opening reaction of an epoxy resin due to a thermal reaction, so distortion and curing shrinkage can be suppressed compared to the case where curing proceeds by a photoradical reaction.
  • the non-irradiated portion is removed by alkali development to form a negative patterned insulating film.
  • the developing method can be a dipping method, a shower method, a spray method, a brush method, or the like.
  • Aqueous alkaline solutions such as amines can be used.
  • the resin layer is completely heat-cured to obtain a highly reliable coating film.
  • the heating temperature is, for example, 140.degree. C. to 180.degree.
  • the heating time is, for example, 20 to 120 minutes.
  • light irradiation may be performed before or after post-curing.
  • the laminate structure of the present invention is preferably used for forming a cured film on a printed wiring board, more preferably for forming a permanent film, and more preferably for a semiconductor package or the like. , solder resists, interlayer dielectric layers, and coverlays. Further, according to the curable resin composition of the present invention, it is possible to obtain a cured product having excellent crack resistance. It can be suitably used for forming a permanent coating film such as a solder resist used for.
  • photosensitive resin solution (A-1) having both an ethylenically unsaturated bond and a carboxyl group has a nonvolatile content of 65%, a solid acid value of 100 mgKOH/g, and a weight average molecular weight (Mw) of about was 3,500.
  • a propylene oxide reaction solution of a novolak-type cresol resin was obtained. This was obtained by adding an average of 1.08 mol of alkylene oxide per equivalent of phenolic hydroxyl group.
  • 293.0 g of the alkylene oxide reaction solution of the novolak type cresol resin obtained, 43.2 g of acrylic acid, 11.53 g of methanesulfonic acid, 0.18 g of methylhydroquinone and 252.9 g of toluene were mixed with a stirrer, a thermometer and air.
  • the mixture was charged into a reactor equipped with a blowing tube, air was blown in at a rate of 10 ml/min, and the mixture was reacted at 110° C. for 12 hours while stirring. 12.6 g of water was distilled out as an azeotrope with toluene, which was produced by the reaction. After cooling to room temperature, the resulting reaction solution was neutralized with 35.35 g of a 15% aqueous sodium hydroxide solution and then washed with water. After that, the toluene was removed by an evaporator while replacing it with 118.1 g of diethylene glycol monoethyl ether acetate to obtain a novolac type acrylate resin solution.
  • ⁇ Formation of resin layer (A)> A base material having a copper thickness of 18 ⁇ m formed on the entire surface was prepared, and pretreatment was performed using CZ8108B from MEC. After that, the resin compositions of Examples and Comparative Examples were applied to the pretreated substrate by a method such as screen printing so that the film thickness after drying was the thickness (unit: ⁇ m) shown in Tables 1 and 2. It was coated on the substrate so that Thereafter, the resin layer (A) was formed by drying at 90° C. for 30 minutes in a hot air circulating drying oven.
  • each resin composition of Examples and Comparative Examples is dried by a method such as screen printing, and the film thickness after drying is the thickness in Tables 1 and 2 (unit: : ⁇ m). Then, it was dried in a hot air circulation drying oven at 90° C./30 minutes to form a resin layer (B).
  • each resin composition of Examples and Comparative Examples was diluted with an organic solvent to adjust the viscosity to an appropriate level.
  • Each resin composition was applied and dried to form a resin layer (B), and a resin layer (A) was formed thereon to prepare a dry film.
  • the carrier film was peeled off after laminating so that the resin layer (A) side was in contact with the base material using a laminator or the like.
  • each laminated structure (two resin layers) on the obtained substrate was exposed from the resin layer (B) side through a step tablet, and after performing the PEB process, before developing the formed pattern
  • the coating thickness of the two resin layers is 100%
  • the largest value of the number of steps at which the coating thickness of 95% or more remains after the exposure, the PEB process, and the development Residual sensitivity was defined as the maximum value of the number of steps at which the coating thickness after development was 5% or less when the coating thickness before development was 100%.
  • the coating film thickness of the pattern formed before and after development is JIS K 5600-1-7: 2014, it was measured as the difference between the measured value obtained as the thickness of the entire coating film and the measured value obtained as the thickness of the substrate.
  • the measurement method is a mechanical measurement method using a thickness measuring device (DIGIMICRO MF-501, manufactured by Nikon Corporation) to measure each laminated structure formed on the base material from the resin layer (B) side with a step tablet. After performing the PEB process at 90 ° C.
  • the coating thickness of the formed pattern before development, and the remaining formed after the exposure, after performing the PEB process, and after development The coating thickness of each coating film is measured, and when the coating thickness before development is taken as 100%, the largest value of the number of steps at which 95% or more of the coating thickness remains after the development is taken as the gloss sensitivity, Residual sensitivity was defined as the largest number of steps at which the coating thickness was 5% or less after development when the coating thickness before development was 100%.
  • ⁇ TCT crack resistance (thermal shock resistance)>
  • the resin composition of each example and each comparative example was formed on an evaluation substrate made of a BT material, and a final test was conducted to evaluate the crack resistance.
  • the exposure process was performed under the conditions of the evaluation method for ⁇ sensitivity> described above, and the PEB process was performed at 90°C for 30 minutes. ⁇ A blanking pattern was formed.
  • the coating film is cured under the conditions of 150 ° C. for 60 minutes in a post-cure process, and the resulting evaluation substrate is subjected to -65 ° C. (30 min.) + 175 ° C. (30 min.) with a thermal shock tester (manufactured by Kusumoto Kasei Co., Ltd.).
  • crack incidence rate is less than 10%
  • ⁇ crack incidence rate is 10% or more and less than 20%
  • ⁇ crack incidence rate is 20% or more and less than 40%
  • ⁇ crack incidence rate is 40% or more
  • ⁇ Photopatternability> The resin composition of each example and each comparative example was formed on a copper-clad substrate, and in order to evaluate the photopatternability, an exposure step was performed under the conditions of the evaluation method for ⁇ sensitivity> described above, and PEB was performed at 90° C. for 30 minutes. After performing the process, a development process (30° C., 0.2 MPa, 1 mass % Na2CO3 aqueous solution) was performed to form an SRO pattern from ⁇ 40 ⁇ m to ⁇ 200 ⁇ m in increments of 10 ⁇ m. In addition, the coating film was cured under the conditions of 150° C.

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  • Engineering & Computer Science (AREA)
  • General Physics & Mathematics (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Architecture (AREA)
  • Structural Engineering (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials For Photolithography (AREA)

Abstract

L'invention concerne une structure stratifiée qui non seulement permet d'atteindre à la fois des caractéristiques contradictoires telles que la résistance au B-HAST et la résistance à la fissuration à un niveau élevé, mais présente également d'excellentes propriétés de formation de motifs par photo-exposition.　Une structure stratifiée ayant une couche de résine à double couche obtenue par stratification d'une couche de résine (A) formée à partir d'une composition de résine (a) et d'une couche de résine (B) formée à partir d'une composition de résine (b), la structure stratifiée étant caractérisée en ce que : la composition de résine (b) de la couche de résine (B) comprend une résine soluble dans les alcalis, un générateur de photo-base qui fonctionne également comme un initiateur de photopolymérisation ou un initiateur de photopolymérisation et un générateur de photo-base, et une résine thermodurcissable ; la composition de résine (a) de la couche de résine (A) contient une résine contenant un groupe carboxyle et une résine thermodurcissable, et ne contient sensiblement pas d'initiateur de photopolymérisation ; et la différence entre la sensibilité au brillant et la sensibilité résiduelle est au plus 20 étapes telles qu'obtenues par mesure de l'épaisseur de film de revêtement d'un motif formé obtenu par l'utilisation d'une tablette à pas, l'exposition de la résine à deux couches à partir du côté de la couche de résine (B) et la réalisation d'une étape PEB, et l'épaisseur de film de revêtement d'un motif formé obtenu par la réalisation de l'étape de PEB après ladite exposition, puis la réalisation d'une étape de développement.
PCT/JP2022/016968 2021-03-31 2022-03-31 Structure stratifiée, film sec, produit durci et composant électronique WO2022211121A1 (fr)

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Publication number Priority date Publication date Assignee Title
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
WO2016060237A1 (fr) * 2014-10-16 2016-04-21 太陽インキ製造株式会社 Structure stratifiée, film sec, et carte de câblage imprimé souple
WO2019012986A1 (fr) * 2017-07-10 2019-01-17 太陽インキ製造株式会社 Structure multicouche, film sec et panneau de câblage imprimé souple

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JP5183073B2 (ja) 2006-07-10 2013-04-17 太陽ホールディングス株式会社 光硬化性・熱硬化性樹脂組成物、及びその硬化物

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
WO2016060237A1 (fr) * 2014-10-16 2016-04-21 太陽インキ製造株式会社 Structure stratifiée, film sec, et carte de câblage imprimé souple
WO2019012986A1 (fr) * 2017-07-10 2019-01-17 太陽インキ製造株式会社 Structure multicouche, film sec et panneau de câblage imprimé souple

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