WO2024195797A1 - 積層構造体、硬化物、およびプリント配線板 - Google Patents

積層構造体、硬化物、およびプリント配線板 Download PDF

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WO2024195797A1
WO2024195797A1 PCT/JP2024/010790 JP2024010790W WO2024195797A1 WO 2024195797 A1 WO2024195797 A1 WO 2024195797A1 JP 2024010790 W JP2024010790 W JP 2024010790W WO 2024195797 A1 WO2024195797 A1 WO 2024195797A1
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film
resin
laminated structure
resin layer
manufactured
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English (en)
French (fr)
Japanese (ja)
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正樹 佐々木
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Taiyo Holdings Co Ltd
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Taiyo Holdings Co Ltd
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Priority to KR1020257026404A priority Critical patent/KR20250134190A/ko
Priority to CN202480019917.8A priority patent/CN120898175A/zh
Priority to JP2025508579A priority patent/JPWO2024195797A1/ja
Publication of WO2024195797A1 publication Critical patent/WO2024195797A1/ja
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    • 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
    • B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
    • 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
    • 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
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • 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
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/027—Thermal properties
    • 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
    • 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
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/036—Multilayers with layers of different types
    • 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
    • B32B2457/00—Electrical equipment
    • B32B2457/08—PCBs, i.e. printed circuit boards

Definitions

  • the present invention relates to a laminated structure. Furthermore, the present invention relates to a cured product formed using the laminated structure and a printed wiring board including the cured product.
  • solder resist layer is formed on the circuit board in areas other than the connection holes to prevent solder from adhering to unnecessary areas.
  • solder resist layers are mainly formed using a so-called photosolder resist, in which a photosensitive resin composition is applied to a substrate, dried, exposed to light, and developed to form a pattern, and the patterned resin is then heated or irradiated with light to fully harden it.
  • a solder resist layer using a laminated structure (photosensitive film) that has a photosensitive resin layer (photosensitive layer) without using the liquid photosensitive resin composition described above.
  • a laminated structure generally has a photosensitive resin layer formed from a photosensitive resin composition on a support film.
  • Such a laminated structure can be laminated to a wiring board by hot pressing, and before exposure or after exposure from the support film side, the support film is peeled off and development is performed to form a patterned solder resist layer.
  • Patent Document 1 proposes a photosensitive film having a support and at least a photosensitive layer on the support, the photosensitive layer being made of a photosensitive composition containing at least a binder having a crosslinkable group, the residual amount of a catalyst for introducing a crosslinkable group into the binder being 200 ppm or less, the melt viscosity at 24°C being 1.0 x 105 Pa ⁇ s to 1.0 x 107 Pa ⁇ s and the melt viscosity at 60°C to 90°C being 1.0 x 102 Pa ⁇ s to 5.0 x 104 Pa ⁇ s, the winding tension when the photosensitive film is wound into a roll to form a roll body being 1.6 kg/10 cm or more, and the roll body having end face pressers on both end faces. Furthermore, Patent Document 1 describes laminating a photosensitive film having a thin photosensitive layer having a thickness of 30 ⁇ m onto a substrate using a vacuum laminator.
  • the inventors have found that when the photosensitive layer of the photosensitive film is thick (e.g., over 80 ⁇ m), depending on the type of laminator, poor embedding such as air bubbles getting in between the substrate and the photosensitive layer during lamination can occur. Specifically, they have found that when the melt viscosity of the photosensitive resin composition is high on the low temperature side (e.g., 50°C), poor embedding occurs due to insufficient resin flow during lamination using a vacuum roll laminator.
  • the inventors have found that in a laminated structure comprising a first film and a resin layer consisting of a dried coating of a photosensitive resin composition formed on the first film, even when the resin layer is thick, greater than 80 ⁇ m and equal to or less than 300 ⁇ m, by adjusting the melt viscosity of the photosensitive resin composition at 50°C and 100°C, it is possible to provide a laminated structure that can be laminated using both a conveyor-type laminator and a vacuum roll laminator.
  • the present invention is based on this finding.
  • a laminated structure comprising a first film and a resin layer formed on the first film, the resin layer is made of a dried coating film of a photosensitive resin composition,
  • the photosensitive resin composition has a melt viscosity at 50° C. of 1,000 Pa ⁇ s or more and 50,000 Pa ⁇ s or less, and a melt viscosity at 100° C. of 50 Pa ⁇ s or more and 2,000 Pa ⁇ s or less,
  • a laminated structure characterized in that the resin layer has a thickness of more than 80 ⁇ m and not more than 300 ⁇ m.
  • the present invention can provide a laminated structure that can be laminated using both a conveyor-type laminator and a vacuum roll laminator.
  • the present invention can also provide a cured product formed using the laminated structure and a printed wiring board including the cured product.
  • FIG. 1 is a schematic cross-sectional view showing one embodiment of a laminated structure of the present invention.
  • the laminate structure according to the present invention comprises a first film and a resin layer formed on the first film, and may further comprise a second film on the resin layer.
  • FIG. 1 is a schematic cross-sectional view showing one embodiment of the laminated structure according to the present invention.
  • the laminated structure 1 shown in FIG. 1 comprises a first film 10, a resin layer 20 provided on one side of the first film 10, and a second film 30 provided on the side of the resin layer 20 opposite to the side on which the first film 10 is provided.
  • a first film 10 a resin layer 20 provided on one side of the first film 10
  • a second film 30 provided on the side of the resin layer 20 opposite to the side on which the first film 10 is provided.
  • the resin layer is a photosensitive layer which is made of a dried coating film of a photosensitive resin composition and which is cured by irradiation with light.
  • the resin layer is preferably a single layer.
  • the thickness of the resin layer is more than 80 ⁇ m and not more than 300 ⁇ m, preferably 85 ⁇ m or more and 250 ⁇ m or less, and more preferably 90 ⁇ m or more and 200 ⁇ m or less. In the present invention, even if the resin layer has a thick thickness within the above numerical range, lamination is possible using both a conveyor-type laminator and a vacuum roll laminator.
  • the melt viscosity of the photosensitive resin composition at 50° C. is 1000 Pa ⁇ s or more and 50000 Pa ⁇ s or less, preferably 3000 Pa ⁇ s or more and 40000 Pa ⁇ s or less, and more preferably 5000 Pa ⁇ s or more and 30000 Pa ⁇ s or less. , more preferably from 10,000 Pa ⁇ s to 25,000 Pa ⁇ s, and even more preferably from 15,000 Pa ⁇ s to 20,000 Pa ⁇ s.
  • the melt viscosity of the photosensitive resin composition at 100°C is 50 Pa ⁇ s or more and 2000 Pa ⁇ s or less, preferably 100 Pa ⁇ s or more and 1500 Pa ⁇ s or less, and more preferably 150 Pa ⁇ s or more and 1250 Pa ⁇ s or less; More preferably, the viscosity is from 200 Pa ⁇ s to 1000 Pa ⁇ s. If the melt viscosity of the photosensitive resin composition at 50° C. and 100° C. is within the above-mentioned range, even if the resin layer has a large thickness within the above-mentioned range, the composition can be laminated with both a conveyor type laminator and a vacuum roll laminator. Lamination is possible.
  • the melt viscosity of the photosensitive resin composition at 50° C. is a value measured by a dynamic viscoelasticity measuring device which is a rotational rheometer.
  • the ratio of the melt viscosity of the photosensitive resin composition at 50°C to the melt viscosity at 100°C is preferably 10 to 200, more preferably 10 to 100, and even more preferably 10 to 50. If the ratio of the melt viscosity of the photosensitive resin composition at 50°C to the melt viscosity at 100°C is within the above numerical range, the change in melt viscosity due to temperature can be suppressed, and the lamination properties will be good in both a conveyor-type laminator and a vacuum roll laminator.
  • the photosensitive resin composition preferably contains (A) a curable resin, (B) a photopolymerization initiator, and (C) an inorganic filler, and may further contain a photopolymerizable monomer, a colorant, an organic solvent, other additive components, etc.
  • the melt viscosity of the photosensitive resin composition at 50° C. and 100° C. can be adjusted to the above-mentioned suitable numerical range by adjusting the type and amount of each component contained in the photosensitive composition.
  • Each component of the photosensitive resin composition will be described in detail below.
  • the curable resin preferably contains an alkali-soluble resin, and may further contain a thermosetting resin.
  • the alkali-soluble resin has an alkali-soluble group that is soluble in an alkaline aqueous solution.
  • the alkali-soluble group is, for example, any one of a phenolic hydroxyl group, a thiol group, and a carboxyl group.
  • Examples of the alkali-soluble resin include a compound having two or more phenolic hydroxyl groups, a carboxyl group-containing resin, a compound having a phenolic hydroxyl group and a carboxyl group, and a compound having two or more thiol groups.
  • the alkali-soluble resin is a carboxyl group-containing resin or a phenolic resin, the adhesion to the base is improved.
  • carboxyl group-containing resin examples include the compounds (which may be either oligomers or polymers) listed below.
  • Carboxyl group-containing resins obtained by copolymerizing an unsaturated carboxylic acid such as (meth)acrylic acid with an unsaturated group-containing compound such as styrene, ⁇ -methylstyrene, lower alkyl (meth)acrylate, isobutylene, etc.
  • Carboxyl group-containing urethane resins obtained by polyaddition reaction of diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, and aromatic diisocyanates with carboxyl group-containing dialcohol compounds such as dimethylolpropionic acid and dimethylolbutanoic acid, and diol compounds such as polycarbonate polyols, polyether polyols, polyester polyols, polyolefin polyols, acrylic polyols, bisphenol A alkylene oxide adduct diols, and compounds having a phenolic hydroxyl group and an alcoholic hydroxyl group.
  • diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, and aromatic diisocyanates with carboxyl group-containing dialcohol compounds such as dimethylolpropionic acid and dimethyl
  • Terminal carboxyl group-containing urethane resins obtained by reacting an acid anhydride with the terminal of a urethane resin obtained by polyaddition reaction of a diisocyanate compound, such as an aliphatic diisocyanate, a branched aliphatic diisocyanate, an alicyclic diisocyanate, or an aromatic diisocyanate, with a diol compound, such as a polycarbonate-based polyol, a polyether-based polyol, a polyester-based polyol, a polyolefin-based polyol, an acrylic polyol, a bisphenol A-based alkylene oxide adduct diol, or a compound having a phenolic hydroxyl group or an alcoholic hydroxyl group.
  • a diisocyanate compound such as an aliphatic diisocyanate, a branched aliphatic diisocyanate, an alicyclic diisocyanate, or an aromatic diiso
  • Carboxyl group-containing urethane resins obtained by polyaddition reaction of diisocyanates with (meth)acrylates of bifunctional epoxy resins such as bisphenol A type epoxy resins, hydrogenated bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bixylenol type epoxy resins, and biphenol type epoxy resins, or their partial acid anhydride modified products, carboxyl group-containing dialcohol compounds, and diol compounds.
  • bifunctional epoxy resins such as bisphenol A type epoxy resins, hydrogenated bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bixylenol type epoxy resins, and biphenol type epoxy resins, or their partial acid anhydride modified products, carboxyl group-containing dialcohol compounds, and diol compounds.
  • a carboxyl group-containing urethane resin having a terminal (meth)acrylation obtained by adding a compound having one hydroxyl group and one or more (meth)acryloyl groups in the molecule, such as a hydroxyalkyl (meth)acrylate, during the synthesis of the resin (2) or (4) above.
  • a carboxyl group-containing urethane resin having a terminal (meth)acrylation obtained by adding a compound having one isocyanate group and one or more (meth)acryloyl groups in the molecule, such as an equimolar reactant of isophorone diisocyanate and pentaerythritol triacrylate, during the synthesis of the resin (2) or (4) above.
  • a carboxyl group-containing resin (acid-modified epoxy acrylate resin) obtained by reacting a polyfunctional epoxy resin with (meth)acrylic acid and adding a dibasic acid anhydride such as phthalic anhydride, tetrahydrophthalic anhydride, or hexahydrophthalic anhydride to the hydroxyl group present in the side chain.
  • a carboxyl group-containing resin (acid-modified epoxy acrylate resin) obtained by reacting a polyfunctional epoxy resin in which the hydroxyl groups of a difunctional epoxy resin are further epoxidized with epichlorohydrin with (meth)acrylic acid, and then adding a dibasic acid anhydride to the resulting hydroxyl groups.
  • a carboxyl group-containing polyester resin obtained by reacting a polyfunctional oxetane resin with a dicarboxylic acid and adding a dibasic acid anhydride to the resulting primary hydroxyl group.
  • a carboxyl group-containing resin obtained by reacting a compound having multiple phenolic hydroxyl groups in one molecule with an alkylene oxide such as ethylene oxide or propylene oxide, reacting the reaction product obtained with an unsaturated group-containing monocarboxylic acid, and reacting the resulting reaction product with a polybasic acid anhydride.
  • a carboxyl group-containing resin obtained by reacting a compound having multiple phenolic hydroxyl groups in one molecule with a cyclic carbonate compound such as ethylene carbonate or propylene carbonate, reacting the reaction product obtained with an unsaturated group-containing monocarboxylic acid, and reacting the resulting reaction product with a polybasic acid anhydride.
  • a cyclic carbonate compound such as ethylene carbonate or propylene carbonate
  • a carboxyl group-containing resin obtained by reacting an epoxy compound having multiple epoxy groups in one molecule with a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule, such as p-hydroxyphenethyl alcohol, and an unsaturated group-containing monocarboxylic acid, such as (meth)acrylic acid, and then reacting the alcoholic hydroxyl group of the resulting reaction product with a polybasic acid anhydride, such as maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, or adipic anhydride.
  • a polybasic acid anhydride such as maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, or adipic anhydride.
  • a compound having one epoxy group and one or more (meth)acryloyl groups in the molecule such as glycidyl (meth)acrylate, ⁇ -methylglycidyl (meth)acrylate
  • Examples of compounds having a phenolic hydroxyl group include compounds having a biphenyl skeleton or a phenylene skeleton, or both, and phenolic resins having various skeletons synthesized using phenol, orthocresol, paracresol, metacresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, catechol, resorcinol, hydroquinone, methylhydroquinone, 2,6-dimethylhydroquinone, trimethylhydroquinone, pyrogallol, phloroglucinol, etc.
  • Examples of compounds having a phenolic hydroxyl group include well-known and commonly used phenolic resins such as phenol novolac resin, alkylphenol volac resin, bisphenol A novolac resin, dicyclopentadiene type phenolic resin, Xylok type phenolic resin, terpene modified phenolic resin, polyvinylphenols, bisphenol F, bisphenol S type phenolic resin, poly-p-hydroxystyrene, condensation products of naphthol and aldehydes, and condensation products of dihydroxynaphthalene and aldehydes.
  • phenolic resins such as phenol novolac resin, alkylphenol volac resin, bisphenol A novolac resin, dicyclopentadiene type phenolic resin, Xylok type phenolic resin, terpene modified phenolic resin, polyvinylphenols, bisphenol F, bisphenol S type phenolic resin, poly-p-hydroxystyrene, condensation products of naphthol and
  • alkali-soluble resin one of the above compounds can be used alone or two or more of them can be used in combination.
  • (meth)acrylate is a general term for acrylate, methacrylate, and mixtures thereof, and the same applies to other similar expressions.
  • the acid value of the alkali-soluble resin is preferably 30 mgKOH/g or more and 150 mgKOH/g or less.
  • the acid value of the carboxyl group-containing photosensitive resin 30 mgKOH/g or more, alkaline development is improved.
  • the acid value 150 mgKOH/g or less it becomes easier to draw a good resist pattern.
  • the weight-average molecular weight of the alkali-soluble resin varies depending on the resin skeleton, but is generally preferably 2,000 to 150,000. By making the weight-average molecular weight 2,000 or more, it is possible to improve tack-free performance and resolution. Furthermore, by making the weight-average molecular weight 150,000 or less, it is possible to improve developability and storage stability.
  • the amount of the alkali-soluble resin is, in terms of solid content, preferably 30% by mass to 70% by mass, more preferably 35% by mass to 60% by mass, based on the total amount of the photosensitive resin composition. If the amount of the alkali-soluble resin is within the above range, it is possible to remove the unexposed areas without leaving any residue during development, resulting in good resolution.
  • thermosetting resin may be any resin that reacts with the functional group of the curable resin by heating and cures to exhibit electrical insulation, and examples of such resins include epoxy compounds, oxetane compounds, melamine resins, silicone resins, etc.
  • epoxy compounds and oxetane compounds can be preferably used, and these may be used in combination.
  • epoxy compound known and commonly used compounds having one or more epoxy groups can be used, and among them, compounds having two or more epoxy groups are preferred.
  • examples include monoepoxy compounds such as butyl glycidyl ether, phenyl glycidyl ether, and glycidyl (meth)acrylate, bisphenol A type epoxy resins, bisphenol S type epoxy resins, bisphenol F type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, alicyclic epoxy resins, trimethylolpropane polyglycidyl ether, phenyl-1,3-diglycidyl ether, biphenyl-4,4'-diglycidyl ether, 1,6-hexanediol diglycidyl ether, diglycidyl ether of ethylene glycol or propylene glycol, sorbitol polyglycidyl ether, tris(2,3-epoxypropyl)isocyanurate, and
  • trihydroxyphenylmethane type epoxy resins such as EPPN-501 and EPPN-502 (all trade names) manufactured by Kayaku Co., Ltd.; bixylenol type or biphenol type epoxy resins or mixtures thereof such as YL-6056, YX-4000, YL-6121 (all trade names) manufactured by Mitsubishi Chemical Corporation; bisphenol S type epoxy resins such as EBPS-200 manufactured by Nippon Kayaku Co., Ltd., EPX-30 manufactured by ADEKA Corporation, and EXA-1514 (trade name) manufactured by DIC Corporation; bisphenol A novolac type epoxy resins such as jER157S (trade name) manufactured by Mitsubishi Chemical Corporation; tetraphenylolethane type epoxy resins such as jERYL-931 (all trade names) manufactured by Mitsubishi Chemical Corporation; heterocyclic epoxy resins such as TEPIC (all trade names) manufactured by Nissan Chemical Co., Ltd.; BLEMMER manufactured by NOF Corporation diglycidyl phthalate resins such as POLY-DGT
  • oxetane compounds include 3-ethyl-3-hydroxymethyloxetane (OXT-101, manufactured by Toagosei Co., Ltd.), 3-ethyl-3-(phenoxymethyl)oxetane (OXT-211, manufactured by Toagosei Co., Ltd.), 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane (OXT-212, manufactured by Toagosei Co., Ltd.), 1,4-bis ⁇ [(3-ethyl-3-oxetanyl)methoxy]methyl ⁇ benzene (OXT-121, manufactured by Toagosei Co., Ltd.), and bis(3-ethyl-3-oxetanylmethyl)ether (OXT-221, manufactured by Toagosei Co., Ltd.). Further examples include phenol novolac-type oxetane compounds. These oxetane compounds may be 3-
  • the amount of thermosetting resin is preferably 5% by mass or more and 50% by mass or less, and more preferably 10% by mass or more and 40% by mass or less, calculated as solid content, based on the total amount of the photosensitive resin composition. If the amount of thermosetting resin is within the above range, a crosslinked body is appropriately formed after the thermosetting reaction, resulting in good heat resistance, such as solder heat resistance and high-temperature exposure resistance.
  • the photopolymerization initiator is used to react the above-mentioned alkali-soluble resin or the photopolymerizable monomer described below by exposure to light. Any known photopolymerization initiator can be used.
  • the photopolymerization initiator may be used alone or in combination of two or more kinds.
  • photopolymerization initiators include bis-(2,6-dichlorobenzoyl)phenylphosphine oxide, bis-(2,6-dichlorobenzoyl)-2,5-dimethylphenylphosphine oxide, bis-(2,6-dichlorobenzoyl)-4-propylphenylphosphine oxide, bis-(2,6-dichlorobenzoyl)-1-naphthylphosphine oxide, bis-(2,6-dimethoxybenzoyl)phenylphosphine oxide, and bis-(2,6-dimethoxybenzoyl)-2,4,4 Bisacylphosphine oxides such as trimethylpentylphosphine oxide, bis-(2,6-dimethoxybenzoyl)-2,5-dimethylphenylphosphine oxide, and bis-(2,4,6-trimethylbenzoyl)-phenylphosphine oxide; 2,6-dimethoxy
  • benzoins such as benzoin, benzil, benzoin methyl ether, benzoin ethyl ether, benzoin n-propyl ether, benzoin isopropyl ether, and benzoin n-butyl ether; benzoin alkyl ethers; benzophenone, p-methylbenzophenone, Michler's ketone, methylbenzophenone, 4,4'-dichlorobenzophenone, 4,4'-bis ...
  • Benzophenones such as ethylaminobenzophenone; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 2-(dimethylamino)-2-[(4-methylphenyl)methyl)-1-[4-(4 acetophenones such as [1-morpholinyl)phenyl]-1-butanone and N,N-dimethylaminoacetophenone; thioxanthones such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2,
  • ⁇ -aminoacetophenone-based photopolymerization initiators include Omnirad 907, 369, 369E, and 379 manufactured by IGM Resins.
  • Commercially available acylphosphine oxide photopolymerization initiators include Omnirad 819 manufactured by IGM Resins.
  • Commercially available oxime ester photopolymerization initiators include Irgacure OXE01 and OXE02 manufactured by BASF Japan Ltd., N-1919 manufactured by ADEKA Corporation, ADEKA ARCLES NCI-831 and NCI-831E, and TR-PBG-304 manufactured by Changzhou Strong Electronic New Materials Co., Ltd.
  • the amount of photopolymerization initiator is, in terms of solid content, preferably 0.1 to 20 parts by mass, more preferably 0.5 to 18 parts by mass, and even more preferably 1 to 15 parts by mass, relative to 100 parts by mass of alkali-soluble resin.
  • the photocurability of the resin composition is good, and the film properties such as chemical resistance are also good, while when it is 20 parts by mass or less, the light absorption at the surface of the resist film (cured film) is good, and the deep curing property is less likely to decrease.
  • a photoinitiator assistant or sensitizer may be used in combination with the above-mentioned photopolymerization initiator.
  • the photoinitiator assistant or sensitizer include benzoin compounds, anthraquinone compounds, thioxanthone compounds, ketal compounds, benzophenone compounds, tertiary amine compounds, and xanthone compounds.
  • thioxanthone compounds such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, and 4-isopropylthioxanthone.
  • thioxanthone compound can improve deep curing properties.
  • These compounds may be used as photopolymerization initiators, but are preferably used in combination with a photopolymerization initiator.
  • the photoinitiator assistant or sensitizer may be used alone or in combination of two or more types.
  • the photopolymerizable monomer is a monomer having an ethylenically unsaturated double bond.
  • a known and commonly used photopolymerizable oligomer, a photopolymerizable vinyl monomer, etc. can be used as such a photopolymerizable monomer.
  • One type of photopolymerizable monomer may be used alone, or two or more types may be used in combination.
  • the photopolymerizable monomer can also be used as a reactive diluent to adjust the viscosity of the photosensitive resin composition.
  • Examples of photopolymerizable oligomers include unsaturated polyester oligomers and (meth)acrylate oligomers.
  • Examples of (meth)acrylate oligomers include epoxy (meth)acrylates such as phenol novolac epoxy (meth)acrylate, cresol novolac epoxy (meth)acrylate, and bisphenol-type epoxy (meth)acrylate, as well as urethane (meth)acrylate, epoxy urethane (meth)acrylate, polyester (meth)acrylate, polyether (meth)acrylate, and polybutadiene-modified (meth)acrylate.
  • (meth)acrylate is a general term for acrylate, methacrylate, and mixtures thereof, and the same applies to other similar expressions.
  • the photopolymerizable vinyl monomer may be any of the known and commonly used ones, for example, polyfunctional allyl compounds such as triallyl isocyanurate, diallyl phthalate, and diallyl isophthalate; alkylene polyol poly(meth)acrylates such as ethylene glycol di(meth)acrylate, butanediol di(meth)acrylates, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and dipentaerythritol hexa(meth)acrylate; ) acrylates; polyoxyalkylene glycol poly(meth)acrylates such as diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, ethoxylated trimethylolpropane triacrylate,
  • the amount of photopolymerizable monomer is preferably 1 to 50 parts by mass, and more preferably 5 to 45 parts by mass, calculated as solid content, per 100 parts by mass of alkali-soluble resin. If the amount of photopolymerizable monomer is within the above range, the exposed area will be sufficiently cured and will have sufficient development resistance during development, resulting in good resolution.
  • the inorganic filler may be any known inorganic filler, such as silica, crystalline silica, Neuburg silica, aluminum hydroxide, glass powder, talc, clay, magnesium carbonate, calcium carbonate, natural mica, synthetic mica, aluminum hydroxide, barium sulfate, barium titanate, iron oxide, non-fibrous glass, hydrotalcite, mineral wool, aluminum silicate, calcium silicate, zinc oxide, etc.
  • inorganic filler such as silica, crystalline silica, Neuburg silica, aluminum hydroxide, glass powder, talc, clay, magnesium carbonate, calcium carbonate, natural mica, synthetic mica, aluminum hydroxide, barium sulfate, barium titanate, iron oxide, non-fibrous glass, hydrotalcite, mineral wool, aluminum silicate, calcium silicate, zinc oxide, etc.
  • the inorganic filler may be surface-treated to enhance dispersibility in the photosensitive resin composition.
  • a surface-treated filler By using a surface-treated filler, aggregation can be suppressed.
  • the surface treatment method There are no particular limitations on the surface treatment method, and any known, commonly used method may be used. However, it is preferable to treat the surface of the inorganic filler with a surface treatment agent having a curable reactive group, such as a coupling agent having a curable reactive group as an organic group.
  • silane-based, titanate-based, aluminate-based, zircoaluminate-based, and other coupling agents can be used.
  • silane-based coupling agents are preferred.
  • examples of such silane-based coupling agents include vinyltrimethoxysilane, vinyltriethoxysilane, N-(2-aminomethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-anilinopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-mercaptopropyl
  • silane-based coupling agents are immobilized in advance on the surface of the filler by adsorption or reaction.
  • the amount of coupling agent to be treated per 100 parts by mass of inorganic filler is preferably 0.5 to 10 parts by mass.
  • the amount of inorganic filler, calculated as solid content, is preferably 1 part by mass or more and 300 parts by mass or less, and more preferably 5 parts by mass or more and 150 parts by mass or less, per 100 parts by mass of alkali-soluble resin. If the amount of inorganic filler is within the above range, the thermal properties such as solder heat resistance and high-temperature exposure resistance will be good.
  • colorant a known colorant such as red, blue, green, yellow, or black can be used, and any of a pigment, dye, or colorant may be used. From the viewpoint of reducing the environmental load and having little effect on the human body, however, a colorant that does not contain a halogen is preferable.
  • Red colorants include monoazos, disazos, azo lakes, benzimidazolone, perylene, diketopyrrolopyrrole, condensed azos, anthraquinones, and quinacridones, and specific examples include those that have the following Color Index (C.I.; published by The Society of Dyers and Colourists) numbers: [0095]
  • monoazo red colorants include Pigment Red 1, 2, 3, 4, 5, 6, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 112, 114, 146, 147, 151, 170, 184, 187, 188, 193, 210, 245, 253, 258, 266, 267, 268, and 269.
  • disazo red colorants include Pigment Red 37, 38, and 41.
  • Examples of monoazo lake-based red colorants include Pigment Red 48:1, 48:2, 48:3, 48:4, 49:1, 49:2, 50:1, 52:1, 52:2, 53:1, 53:2, 57:1, 58:4, 63:1, 63:2, 64:1, and 68.
  • Examples of benzimidazolone-based red colorants include Pigment Red 171, 175, 176, 185, and 208.
  • Examples of perylene-based red colorants include Solvent Red 135, 179, Pigment Red 123, 149, 166, 178, 179, 190, 194, and 224.
  • Examples of diketopyrrolopyrrole red colorants include Pigment Red 254, 255, 264, 270, and 272.
  • condensed azo red colorants include Pigment Red 220, 144, 166, 214, 220, 221, and 242.
  • examples of anthraquinone red colorants include Pigment Red 168, 177, and 216, Solvent Red 52, 149, 150, and 207.
  • Examples of quinacridone red colorants include Pigment Red 122, 202, 206, 207, and 209.
  • Blue colorants include phthalocyanine and anthraquinone types, and pigment types include compounds classified as pigments, such as Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, and 60.
  • Dye types include Solvent Blue 35, 63, 67, 68, 70, 83, 87, 94, 97, 122, and 136.
  • metal-substituted or unsubstituted phthalocyanine compounds can also be used.
  • yellow colorants examples include monoazo, disazo, condensed azo, benzimidazolone, isoindolinone, and anthraquinone.
  • anthraquinone yellow colorants include Solvent Yellow 163, Pigment Yellow 24, 108, 193, 147, 199, and 202.
  • Isoindolinone yellow colorants include Pigment Yellow 110, 109, 139, 179, and 185.
  • Condensed azo yellow colorants include Pigment Yellow 93, 94, 95, 128, 155, 166, and 180.
  • benzimidazolone yellow colorants examples include Pigment Yellow 120, 151, 154, 156, 175, and 181.
  • Examples of monoazo yellow colorants include Pigment Yellow 1, 2, 3, 4, 5, 6, 9, 10, 12, 61, 62, 62:1, 65, 73, 74, 75, 97, 100, 104, 105, 111, 116, 167, 168, 169, 182, and 183.
  • Examples of disazo yellow colorants include Pigment Yellow 12, 13, 14, 16, 17, 55, 63, 81, 83, 87, 126, 127, 152, 170, 172, 174, 176, 188, and 198.
  • Black colorants include carbon black, Pigment Black 1, 6, 7, 8, 9, 10, 11, 12, 13, 18, 20, 25, 26, 28, 29, 30, 31, 32, etc.
  • Pigment Violet 19 23, 29, 32, 36, 38, and 42
  • Solvent Violet 13 and 36 C.I. Pigment Orange 1, 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 61, 63, 64, 71, and 73
  • Pigment Brown 23 and 25, and titanium oxide examples include Pigment Violet 19, 23, 29, 32, 36, 38, and 42, Solvent Violet 13 and 36, C.I. Pigment Orange 1, 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 61, 63, 64, 71, and 73, Pigment Brown 23 and 25, and titanium oxide.
  • the amount of colorant to be added is not particularly limited, but is preferably 0.1 to 10 parts by mass, calculated as solid content, per 100 parts by mass of the alkali-soluble resin.
  • the photosensitive resin composition may contain an organic solvent to adjust the viscosity.
  • organic solvent include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; glycol ethers such as cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, diethylene glycol monomethyl ether acetate, and tripropylene glycol monomethyl ether; esters such as ethyl acetate, butyl acetate, butyl lactate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether; esters
  • the photosensitive resin composition may further contain, as necessary, components such as elastomers, mercapto compounds, urethanization catalysts, thixotropic agents, adhesion promoters, block copolymers, chain transfer agents, polymerization inhibitors, copper inhibitors, antioxidants, rust inhibitors, thickeners such as organic bentonite and montmorillonite, at least one of silicone-based, fluorine-based, and polymer-based defoamers and leveling agents, and flame retardants such as phosphorus compounds such as phosphinates, phosphate ester derivatives, and phosphazene compounds. These may be known in the field of electronic materials.
  • components such as elastomers, mercapto compounds, urethanization catalysts, thixotropic agents, adhesion promoters, block copolymers, chain transfer agents, polymerization inhibitors, copper inhibitors, antioxidants, rust inhibitors, thickeners such as organic bentonite and montmorillonite, at least one
  • the first film supports the resin layer (i.e., a dried coating film made of a photosensitive resin composition) and adheres to the resin layer when the laminate structure is integrally molded by laminating the laminate structure on a substrate by heating or the like so that the resin layer side of the laminate structure is in contact with the substrate.
  • the first film may be peeled off from the laminate structure in a step after lamination. In the present invention, it is preferable that the first film is peeled off from the laminate structure in a step after exposure.
  • the first film can be any film without particular limitations.
  • polyester films such as polyethylene terephthalate and polyethylene naphthalate, polyimide films, polyamideimide films, polypropylene films, polystyrene films, and other films made of thermoplastic resins can be preferably used.
  • polyester films are preferably used from the viewpoints of optical properties, heat resistance, mechanical strength, ease of handling, etc.
  • the first film may be a single layer, or may be a laminate of two or more layers.
  • thermoplastic resin film described above it is preferable to use a film that has been uniaxially or biaxially stretched in order to improve strength.
  • the thickness of the first film is not particularly limited, but is appropriately selected depending on the application, for example, within the range of 10 to 150 ⁇ m.
  • the laminated structure according to the present invention may have a second film on the other side of the resin layer (the side opposite to the first film) for the purpose of preventing adhesion of dust or the like to the surface of the resin layer and improving handleability.
  • the second film is peeled off from the laminated structure before lamination when the laminated structure is integrally molded by laminating the resin layer side of the laminated structure on a substrate by heating or the like so as to be in contact with the substrate.
  • the second film for example, a film made of the above-mentioned thermoplastic resin can be suitably used, as in the first film.
  • the surface of the second film that comes into contact with the resin layer may be subjected to a release treatment as described above.
  • the thickness of the second film is not particularly limited, but is appropriately selected depending on the application, for example, within the range of 10 to 150 ⁇ m.
  • the surface of the second film that comes into contact with the resin layer may be subjected to a release treatment.
  • the release treatment can be performed by dissolving or dispersing a release agent such as wax, silicone wax, alkyd resin, urethane resin, melamine resin, silicone resin, etc. in an appropriate solvent to prepare a coating liquid, which is then applied to the surface of the second film by a known method such as a coating method such as roll coating or spray coating, gravure printing, or screen printing, and then drying.
  • the cured product of the present invention can be obtained by curing the resin layer (dried coating of the photosensitive resin composition) of the laminated structure.
  • a method for forming a cured product and a method for manufacturing a printed wiring board having the cured product (cured coating) on a substrate on which a circuit pattern is formed will be described.
  • a method for manufacturing a printed wiring board using a laminated structure having a second film will be described.
  • the second film is peeled off from the laminated structure to expose the resin layer
  • the resin layer of the laminated structure is attached to the substrate on which the circuit pattern is formed
  • exposure is performed from the first film of the laminated structure
  • the first film is peeled off from the laminated structure and development is performed to form a patterned resin layer on the substrate
  • the patterned resin layer is cured by light irradiation or heat to form a cured coating, thereby forming a printed wiring board.
  • the second film is peeled off from the laminated structure to expose the resin layer, and the resin layer of the laminated structure is laminated onto a substrate on which a circuit pattern has been formed.
  • Substrates on which a circuit pattern has been formed include printed wiring boards and flexible printed wiring boards on which circuits have been formed in advance, as well as copper-clad laminates of all grades (FR-4, etc.) made of materials such as paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth/non-woven cloth epoxy, glass cloth/paper epoxy, synthetic fiber epoxy, copper-clad laminates for high-frequency circuits made of fluororesin, polyethylene, polyphenylene ether, polyphenylene oxide, cyanate ester, etc., as well as polyimide films, PET films, glass substrates, ceramic substrates, wafer plates, etc.
  • Both conveyor laminators and vacuum roll laminators can be used to bond the resin layer of the laminated structure onto the circuit board.
  • a vacuum roll laminator is a device that continuously laminates a laminated structure onto a substrate in a vacuum.
  • a vacuum roll laminator By using a vacuum roll laminator, it is possible to laminate a laminated structure onto a substrate with unevenness without introducing air bubbles or dust. Furthermore, laminating in a vacuum also eliminates contamination.
  • a vacuum roll laminator By using a vacuum roll laminator, it is possible to manufacture long substrates.
  • the conditions of the vacuum roll laminator can be appropriately adjusted depending on the thickness of the resin layer of the laminated structure and the melt viscosity of the photosensitive resin composition at 50° C. and 100° C.
  • the conditions of the vacuum roll laminator are preferably a temperature of 80 to 90° C., a pressure of 3 to 5 kgf/cm 2 , and a reduced pressure of 10 to 100 Pa.
  • a conveyor-type laminator is a laminator device that is based on single-wafer processing. It bonds a laminated structure to a substrate that fits inside a vacuum chamber, removes air bubbles using a vacuum, and then bonds the substrate by applying pressure, making it possible to bond the laminated structure to an uneven substrate without introducing air bubbles.
  • the conditions for the conveying laminator can be adjusted as appropriate depending on the thickness of the resin layer of the laminated structure and the melt viscosity of the photosensitive resin composition at 50°C and 100°C.
  • the conditions for the conveying laminator are preferably a temperature of 50°C to 80°C, a vacuum time of 10 to 60 seconds, and a pressure time of 20 to 120 seconds.
  • exposure irradiation with active energy rays
  • This process hardens only the exposed resin layer.
  • the exposure process is not particularly limited, and for example, it may be selectively exposed to active energy rays through a photomask on which a desired pattern is formed using a contact (or non-contact) method, or the desired pattern may be exposed to active energy rays using a direct imaging device.
  • the exposure machine used for the active energy ray irradiation may be a machine equipped with a high pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, or the like, and capable of irradiating ultraviolet rays in the range of 350 to 450 nm, and may also be a direct imaging machine (e.g., a laser direct imaging machine that draws an image directly with a laser based on CAD data from a computer).
  • the laser light source of the direct imaging machine may be either a gas laser or a solid laser, so long as it uses a laser beam with a maximum wavelength in the range of 350 to 410 nm.
  • the exposure dose for forming an image varies depending on the film thickness, etc., but may generally be within the range of 20 to 800 mJ/cm 2 , and preferably 20 to 600 mJ/cm 2 .
  • the first film After exposure, the first film is peeled off from the laminated structure and developed to form a patterned resin layer on the substrate.
  • the surface of the exposed and hardened resin layer is imprinted with the shape of the first film surface.
  • the developing process is not particularly limited, and a dipping method, a shower method, a spray method, a brush method, etc. can be used.
  • an alkaline aqueous solution of potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, amines, etc. can be used.
  • the patterned resin layer is cured by irradiation with active energy rays (light) or heat to form a cured product (cured coating).
  • This process is called main curing or additional curing, and promotes polymerization of unreacted monomers in the resin layer, and furthermore, the amount of remaining carboxyl groups can be reduced by thermally curing the carboxyl group-containing photosensitive resin and the epoxy resin.
  • the active energy ray irradiation can be performed in the same manner as the above-mentioned exposure, but it is preferable to perform it under conditions that are stronger than the irradiation energy during exposure. For example, it can be 500 to 3000 mJ/cm 2.
  • the thermal curing can be performed under heating conditions of 100 to 200 ° C. for about 20 to 90 minutes.
  • the main curing is preferably performed by thermal curing after photocuring.
  • the epoxy resin (a) obtained was calculated from the epoxy equivalent, and about 5 of the 6.2 alcoholic hydroxyl groups in the starting material bisphenol F type epoxy resin were epoxidized. 310 parts of this epoxy resin (a) and 282 parts of carbitol acetate were charged in a flask, heated to 90°C, stirred, and dissolved. The resulting solution was once cooled to 60°C, and 72 parts (1 mole) of acrylic acid, 0.5 parts of methylhydroquinone, and 2 parts of triphenylphosphine were added, heated to 100°C, and reacted for about 60 hours to obtain a reaction product with an acid value of 0.2 mgKOH/g.
  • the reaction product was cooled to 80-90°C, 106 parts of tetrahydrophthalic anhydride were added, the mixture was reacted for 8 hours, and the mixture was cooled and then taken out.
  • the acid-modified epoxy acrylate resin thus obtained (acid-modified epoxy acrylate resin A-4) had a solid content of 65%, an acid value of the solid matter of 100 mgKOH/g, and a weight average molecular weight Mw of about 3,500.
  • a polyethylene terephthalate film (“E5041" manufactured by Toyobo Co., Ltd.) having a thickness of 25 ⁇ m was prepared as the first film.
  • Each photosensitive resin composition obtained above was uniformly applied to the surface of the first film by a die coater, and the film was dried by passing through a drying oven at 80°C to 130°C (average 108°C) for 5 minutes to form a resin layer having a thickness of 100 ⁇ m.
  • MA-411 manufactured by Oji F-Tex Co., Ltd., biaxially oriented polypropylene film
  • the obtained laminated structure was wound into a roll (winding length 50 m) and slit to a width of 247 mm to obtain a rolled laminated structure.
  • melt viscosity Measurement Conditions Sensor: ⁇ 20mm parallel plate type Heating rate: 5°C/min Measurement frequency: 1Hz Measurement pressure: 3 Pa
  • ⁇ Evaluation of laminated structure 1> (Lamination ability with conveyor laminator)
  • the laminated structure obtained above is cut to a predetermined size, and the second film is peeled off.
  • a conveying type vacuum laminator manufactured by Nikko Materials Co., Ltd., CVP-300
  • the laminated structure obtained above was set in a vacuum roll laminator ("MVRN-DFW-500TP" manufactured by MCK Corporation).
  • the lamination conditions were: vacuum degree: 50 Pa, substrate tension: 50 N, substrate preheating temperature: 80 ° C., lamination roll temperature: 90 ° C., lamination pressure: 0.4 MPa, conveying speed: 0.5 m / min, dry film unwinding tension: 20 N, separator winding tension: 15 N.
  • the state after lamination was observed with an optical microscope and evaluated according to the following criteria.
  • the evaluation results are shown in Table 2.
  • the evaluation was performed according to the following criteria.
  • the evaluation results are shown in Table 2. [Evaluation Criteria] ⁇ : No abnormalities (no voids due to poor filling or air bubbles due to air traps) ⁇ : Abnormal (voids due to poor filling or air bubbles due to air traps)
  • the laminated structures of Examples 1 to 3 exhibit good lamination properties with both a conveyor-type laminator and a vacuum roll laminator, whereas when the melt viscosity is too low as in Comparative Example 1, fusion occurs before the specified degree of vacuum is reached, resulting in a state in which air is trapped (a so-called air trap), causing poor lamination. Also, lamination was attempted with a vacuum roll laminator for Comparative Example 1, but the peelability of the second film deteriorated due to the melt viscosity being too low, making lamination impossible and therefore evaluation was not possible.

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  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • General Physics & Mathematics (AREA)
  • Fluid Mechanics (AREA)
  • Thermal Sciences (AREA)
  • Non-Metallic Protective Coatings For Printed Circuits (AREA)
  • Materials For Photolithography (AREA)
  • Laminated Bodies (AREA)
PCT/JP2024/010790 2023-03-20 2024-03-19 積層構造体、硬化物、およびプリント配線板 Ceased WO2024195797A1 (ja)

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