WO2022114175A1 - Composition de résine photosensible - Google Patents

Composition de résine photosensible Download PDF

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Publication number
WO2022114175A1
WO2022114175A1 PCT/JP2021/043588 JP2021043588W WO2022114175A1 WO 2022114175 A1 WO2022114175 A1 WO 2022114175A1 JP 2021043588 W JP2021043588 W JP 2021043588W WO 2022114175 A1 WO2022114175 A1 WO 2022114175A1
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WIPO (PCT)
Prior art keywords
silica
photosensitive resin
mass
resin composition
modified
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PCT/JP2021/043588
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English (en)
Japanese (ja)
Inventor
将暢 石坂
諒哉 ▲高▼島
Original Assignee
株式会社タムラ製作所
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Application filed by 株式会社タムラ製作所 filed Critical 株式会社タムラ製作所
Priority to CN202180080124.3A priority Critical patent/CN116602060A/zh
Publication of WO2022114175A1 publication Critical patent/WO2022114175A1/fr

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    • 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
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings

Definitions

  • the present invention has a photosensitive resin composition and a coating film of a photosensitive resin composition suitable for a coating material, for example, a coating material for coating a conductor circuit pattern formed on a wiring board such as a flexible printed wiring board.
  • the present invention relates to a wiring board having a dry film and a photocurable film of a photosensitive resin composition.
  • the printed wiring board is used to form a conductor circuit pattern on the board and mount electronic components on the soldering lands of the pattern by soldering, and the circuit part excluding the soldering lands is an insulating protective film (for example, it is coated with a solder resist film).
  • This insulating protective film can be obtained, for example, by applying a photosensitive resin composition to a printed wiring board to form a coating film, and then photocuring the coating film. This prevents the solder from adhering to unnecessary parts when soldering electronic components to the printed wiring board, and also prevents the circuit from being directly exposed to air and corroded by oxidation and humidity. ..
  • urethane beads may be blended as an organic filler in the photosensitive resin composition (Patent Document 1).
  • urethane beads when urethane beads are blended in the photosensitive resin composition, the urethane beads have a low softening point, so that the solid content aggregates during storage and storage of the photosensitive resin composition, and the dispersibility of the photosensitive resin composition There was a problem that it may not be obtained. Therefore, by blending silica-coated urethane beads, in which urethane beads are coated with silica, into the photosensitive resin composition, flexibility (bending property) is imparted to the insulating protective film, and dispersibility is provided in the photosensitive resin composition. It is also given.
  • the silica of the silica-coated urethane beads is untreated silica that has not been surface-treated, and if the amount of silica coated on the silica-coated urethane beads is increased in order to obtain the dispersibility of the photosensitive resin composition, the silica-coated urethane beads become Water absorption is imparted, and there is a risk that the insulation reliability of the insulating protective film may be impaired, especially in an environment of high temperature and high humidity.
  • the present invention is a photosensitive resin composition, the photosensitive resin, which is excellent in dispersibility during storage and storage, can reduce water absorption, and can form a cured film having excellent bendability and insulation reliability. It is an object of the present invention to provide a dry film having a coating film of the composition and a wiring board having a photocurable film of the photosensitive resin composition.
  • the gist of the structure of the present invention is as follows. [1] Containing (A) a carboxyl group-containing photosensitive resin, (B) an epoxy compound, (C) urethane beads, (D) a photopolymerization initiator, and (E) a reactive diluent. A photosensitive resin composition in which the urethane beads (C) are coated with silica, and 20% by mass or more of the 100% by mass of the silica is hydrophobic silica. [2] The photosensitive resin composition according to [1], wherein 30% by mass or more of the 100% by mass of the silica is hydrophobic silica.
  • the hydrophobic silica is surface-modified with a monoalkylsilylated silica surface-modified with a monoalkylsilyl group, a dialkylsiloxylated silica surface-modified with a dialkylsilyl group, and a surface modification with a trialkylsilyl group.
  • the photosensitive resin composition according to any one of [1] to [4], which is at least one selected from the group consisting of surface-modified silica.
  • the hydrophobic silica is a monoalkyl siroxylated silica surface-modified with a monoalkyl silyl group, a dialkyl siroxylated silica surface-modified with a dialkyl silyl group, or a (meth) acrylic silyl group.
  • [7] [1] to [6] contain 35 parts by mass or more and 150 parts by mass or less of the (C) urethane beads coated with silica with respect to 100 parts by mass of the (A) carboxyl group-containing photosensitive resin.
  • silica coverage means the ratio of the mass of silica coated on the outer surface of the urethane beads to the mass of the urethane beads coated with silica.
  • the coverage of silica can be determined by weighing the ash content of the urethane beads coated with silica after burning them at 600 ° C. for 2 hours.
  • (C) urethane beads are coated with silica, and 20% by mass or more of the 100% by mass of the silica is hydrophobic silica, so that water absorption is excellent while being excellent in dispersibility during storage and storage.
  • a photosensitive resin composition capable of reducing the rate can be obtained, and a photosensitive resin composition capable of forming a cured film having excellent bendability and insulation reliability can be obtained.
  • the urethane beads (C) is hydrophobic silica, the water absorption rate of the photosensitive resin composition can be further reduced. A cured film with even better insulation reliability can be formed.
  • the coverage of the silica of the urethane beads (C) is 1.0% by mass or more and 40% by mass or less, so that the photosensitive resin composition having excellent dispersibility during storage and storage is more reliable. It is possible to obtain a photosensitive resin composition capable of obtaining a product and more reliably forming a cured film having excellent bendability.
  • the coverage of the silica of the urethane beads (C) is 5.0% by mass or more and 30% by mass or less, so that the photosensitive resin composition having excellent dispersibility during storage and storage is more reliably performed. It is possible to obtain a product, and more reliably, to obtain a photosensitive resin composition capable of forming a cured film having excellent bendability.
  • the hydrophobic silica is surface-modified with a monoalkylsilyl group, monoalkylsiloxylated silica, surface-modified with a dialkylsilyl group, dialkylsiloxylated silica, or trialkylsilyl.
  • a photosensitive resin composition that can more reliably reduce the water absorption rate while having excellent dispersibility during storage and storage by being at least one selected from the group consisting of silica surface-modified with a polysiloxane group. It is also possible to obtain a photosensitive resin composition capable of more reliably forming a cured film having excellent bendability and insulation reliability.
  • the hydrophobic silica is surface-modified with a monoalkylsilyl group, monoalkylsiloxylated silica, and surface-modified with a dialkylsilyl group, dialkylsiloxylated silica, (meth).
  • a monoalkylsilyl group monoalkylsiloxylated silica
  • dialkylsilyl group dialkylsiloxylated silica, (meth)
  • the water absorption rate can be further reliably improved while being excellent in dispersibility during storage and storage.
  • a photosensitive resin composition that can be reduced can be obtained, and a photosensitive resin composition that can more reliably form a cured film having excellent bendability and insulation reliability can be obtained.
  • the photosensitive resin is contained by containing 35 parts by mass or more and 150 parts by mass or less of (C) urethane beads coated with silica with respect to 100 parts by mass of (A) carboxyl group-containing photosensitive resin. It is possible to obtain a photosensitive resin composition that can reduce the water absorption rate while imparting excellent coatability to the composition and more reliably with excellent dispersibility during storage and storage, and more reliably with bending. It is possible to obtain a photosensitive resin composition capable of forming a cured film having excellent properties and insulation reliability.
  • the photosensitive resin composition of the present invention comprises (A) a carboxyl group-containing photosensitive resin, (B) an epoxy compound, (C) urethane beads, (D) a photopolymerization initiator, and (E) a reactive dilution.
  • the (C) urethane bead is coated with silica, and 20% by mass or more of the 100% by mass of the silica is hydrophobic silica.
  • the structure of the carboxyl group-containing photosensitive resin of the component (A) is not particularly limited, and examples thereof include a resin having one or more photosensitive unsaturated double bonds and a free carboxyl group.
  • the carboxyl group-containing photosensitive resin for example, acrylic acid or methacrylic acid (hereinafter, “(meth) acrylic acid”) may be added to at least a part of the epoxy group of the polyfunctional epoxy resin having two or more epoxy groups in one molecule.
  • the radically polymerizable unsaturated monocarboxylic acid produced by reacting with a radically polymerizable unsaturated monocarboxylic acid such as) to obtain a radically polymerizable unsaturated monocarboxylic oxide epoxy resin such as epoxy (meth) acrylate.
  • a polybasic acid-modified radically polymerizable unsaturated monocarboxylic oxide epoxy resin such as a polybasic acid-modified epoxy (meth) acrylate obtained by reacting a hydroxyl group of a carboxylic oxide epoxy resin with a polybasic acid and / or its anhydride. And so on.
  • the chemical structure of the polyfunctional epoxy resin is not particularly limited as long as it is a bifunctional or higher functional epoxy resin.
  • the epoxy equivalent of the polyfunctional epoxy resin is not particularly limited, and for example, the upper limit thereof is preferably 4000 g / eq, more preferably 3000 g / eq, still more preferably 2500 g / eq, and particularly preferably 2000 g / eq.
  • the lower limit of the epoxy equivalent of the polyfunctional epoxy resin is preferably 100 g / eq, and particularly preferably 200 g / eq.
  • Examples of the resin type of the polyfunctional epoxy resin include rubber-modified epoxy such as biphenyl aralkyl type epoxy resin, phenyl aralkyl type epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin, and silicone-modified epoxy resin.
  • rubber-modified epoxy such as biphenyl aralkyl type epoxy resin, phenyl aralkyl type epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin, and silicone-modified epoxy resin.
  • Phenol novolak type epoxy resin such as resin, ⁇ -caprolactone modified epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, cresol novolak type epoxy resin such as ortho-cresol novolak type epoxy resin, bisphenol A novolak type epoxy resin, Cyclic aliphatic polyfunctional epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, heterocyclic epoxy resin, bisphenol-modified novolak type epoxy resin, polyfunctional modified novolak type epoxy resin and the like can be mentioned. Further, those epoxy resins in which halogen atoms such as Br and Cl are further introduced may be used. These polyfunctional epoxy resins may be used alone or in combination of two or more.
  • the radically polymerizable unsaturated monocarboxylic acid is not particularly limited, and examples thereof include (meth) acrylic acid, crotonic acid, tiglic acid, angelic acid, and cinnamon acid. Of these, (meth) acrylic acid is preferred because it is easy to obtain and handle. These radically polymerizable unsaturated monocarboxylic acids may be used alone or in combination of two or more.
  • the method for reacting the polyfunctional epoxy resin with the radically polymerizable unsaturated monocarboxylic acid is not particularly limited, and for example, the polyfunctional epoxy resin and the radically polymerizable unsaturated monocarboxylic acid are mixed in a diluent such as an organic solvent. Examples thereof include a method of dissolving and stirring while heating.
  • a radically polymerizable unsaturated monocarboxylic oxide epoxy resin by an addition reaction of a polybasic acid and / or a polybasic acid anhydride to a hydroxyl group generated by a reaction between a polyfunctional epoxy resin and a radically polymerizable unsaturated monocarboxylic acid.
  • a free carboxyl group is introduced into the.
  • the chemical structure of the polybasic acid and the polybasic acid anhydride is not particularly limited, and either saturated or unsaturated can be used.
  • polybasic acid examples include succinic acid, maleic acid, adipic acid, citric acid, phthalic acid, tetrahydrophthalic acid, 3-methyltetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, 3-ethyltetrahydrophthalic acid, 4-.
  • Tetrahydrophthalates such as ethyltetrahydrophthalic acid, endomethylenetetrahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, hexahydrophthalic acid, 3-methylhexahydrophthalic acid, 4-methylhexahydrophthalic acid, 3-ethylhexahydrophthalic acid
  • examples thereof include acids, hexahydrophthalic acids such as 4-ethylhexahydrophthalic acid, trimellitic acid, pyromellitic acid and diglycolic acid.
  • the polybasic acid anhydride include the above-mentioned various polybasic acid anhydrides. These polybasic acids and / or polybasic acid anhydrides may be used alone or in combination of two or more.
  • the method for reacting the radically polymerizable unsaturated monocarboxylic oxide epoxy resin with the polybasic acid and / or the polybasic acid anhydride is not particularly limited, and for example, the radically polymerizable unsaturated monocarboxylic oxide epoxy resin and the polybasic acid are not particularly limited. And / or a method of dissolving the polybasic acid anhydride in a diluent such as an organic solvent and stirring while heating can be mentioned.
  • the above-mentioned polybasic acid-modified unsaturated monocarboxylic oxide epoxy resin can also be used as a carboxyl group-containing photosensitive resin, but a part of the carboxyl groups of the polybasic acid-modified unsaturated monocarboxylic oxide epoxy resin obtained as described above.
  • a polybasic acid-modified radically polymerizable unsaturated monocarboxylic oxide epoxy obtained by further introducing a radically polymerizable unsaturated group, which is obtained by an addition reaction of a compound having one or more radically polymerizable unsaturated groups and an epoxy group. Resin may be used.
  • the polybasic acid-modified radically polymerizable unsaturated monocarboxylic oxide epoxy resin further introduced with a radically polymerizable unsaturated group has a radically polymerizable unsaturated group further introduced into the side chain of the polybasic acid modified unsaturated monocarboxylic oxide epoxy resin. It is a carboxyl group-containing photosensitive resin having further improved photosensitivity as compared with the polybasic acid-modified unsaturated monocarboxylic oxide epoxy resin because of the chemical structure.
  • Examples of the compound having one or more radically polymerizable unsaturated groups and an epoxy group include glycidyl compounds.
  • Examples of the glycidyl compound include glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, pentaerythritol triacrylate monoglycidyl ether, pentaerythritol trimethacrylate monoglycidyl ether and the like.
  • One molecule may have one glycidyl group or a plurality of glycidyl groups.
  • the compound having one or more radically polymerizable unsaturated groups and an epoxy group described above may be used alone or in combination of two or more.
  • the method for reacting the polybasic acid-modified unsaturated monocarboxylic oxide epoxy resin with a compound having one or more radically polymerizable unsaturated groups such as a glycidyl compound and an epoxy group is not particularly limited, and is not particularly limited, for example, many.
  • a method of dissolving a basic acid-modified unsaturated monocarboxylic oxide epoxy resin and a compound having one or more radically polymerizable unsaturated groups and an epoxy group in a diluent such as an organic solvent and stirring while heating is mentioned. Be done.
  • the acid value of the carboxyl group-containing photosensitive resin is not particularly limited, and for example, the lower limit thereof is preferably 30 mgKOH / g and particularly preferably 40 mgKOH / g from the viewpoint of reliably imparting alkali developability.
  • the upper limit of the acid value of the carboxyl group-containing photosensitive resin is preferably 200 mgKOH / g from the viewpoint of preventing dissolution of the exposed portion (photocuring portion) by the alkaline developer, and the moisture resistance and insulation reliability of the photocured product are preferable.
  • 150 mgKOH / g is particularly preferable from the viewpoint of surely preventing the decrease of the amount.
  • the mass average molecular weight of the carboxyl group-containing photosensitive resin is not particularly limited, and for example, the lower limit thereof is preferably 6000, more preferably 7000 from the viewpoint of reliably obtaining the toughness and dryness to the touch of the photocured product. 8000 is particularly preferable.
  • the upper limit of the mass average molecular weight of the carboxyl group-containing photosensitive resin is preferably 200,000, more preferably 100,000, and particularly preferably 50,000, for example, from the viewpoint of surely obtaining good alkali developability.
  • the "mass average molecular weight” means a mass average molecular weight measured at room temperature using gel permeation chromatography (GPC) and calculated in terms of polystyrene.
  • the carboxyl group-containing photosensitive resin may be prepared in the above reaction step using each of the above components, or a commercially available carboxyl group-containing photosensitive resin may be used.
  • Examples of the carboxyl group-containing photosensitive resin on the market include “SP-4621” (Showa Denko KK), "KAYARAD ZAR-2000", “KAYARAD ZFR-1122", “KAYARAD FLX-2089", and “KAYARAD”.
  • "ZCR-1569H” aboveve, Nippon Kayaku Co., Ltd.
  • Cyclomer P (ACA) Z-250” (Dycel Ornex Co., Ltd.) can be mentioned.
  • These carboxyl group-containing photosensitive resins may be used alone or in combination of two or more.
  • the epoxy compound of the component (B) is for increasing the crosslink density of the cured product of the photosensitive resin composition and imparting sufficient strength to the cured product.
  • the epoxy compound include epoxy resins.
  • the epoxy resin include the same epoxy resin as the polyfunctional epoxy resin used for preparing the above-mentioned carboxyl group-containing photosensitive resin.
  • rubber-modified epoxy resins such as biphenyl aralkyl type epoxy resin, phenyl aralkyl type epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin, silicone-modified epoxy resin, and ⁇ -caprolactone.
  • Phenol novolak type epoxy resin such as modified epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, cresol novolak type epoxy resin such as ortho-cresol novolak type epoxy resin, bisphenol A novolak type epoxy resin, cyclic aliphatic polyfunctional Examples thereof include an epoxy resin, a glycidyl ester type polyfunctional epoxy resin, a glycidylamine type polyfunctional epoxy resin, a heterocyclic polyfunctional epoxy resin, a bisphenol-modified novolak type epoxy resin, and a polyfunctional modified novolak type epoxy resin. These epoxy compounds may be used alone or in combination of two or more.
  • the content of the epoxy compound is not particularly limited, but for example, 100 parts by mass of the carboxyl group-containing photosensitive resin (solid content, the same applies hereinafter) from the viewpoint of obtaining a coating film having sufficient strength after curing of the photosensitive resin composition.
  • 10 parts by mass or more and 100 parts by mass or less are preferable, and 10 parts by mass or more and 50 parts by mass or less are particularly preferable.
  • the urethane beads of the component (C) are particulate matter in which at least a part of the outer surface thereof is coated with silica. Therefore, the urethane beads of the component (C) have a core-shell structure in which the urethane beads form the core portion and the silica forms the shell portion in at least a part of the outer surface. Further, 20% by mass or more of the total silica covering the outer surface of the urethane beads is hydrophobic silica. That is, 20% by mass or more of 100% by mass of silica is composed of hydrophobic silica.
  • the urethane beads are coated with silica, and 20% by mass or more of the 100% by mass of the silica is hydrophobic silica, so that the photosensitive resin composition has excellent dispersibility during storage and storage, and also. , The water absorption rate is reduced. Further, since the urethane beads (C) are coated with silica and 20% by mass or more of the 100% by mass of the silica is hydrophobic silica, the photosensitive resin composition is excellent in bendability and insulation reliability. A cured film can be formed.
  • the proportion of hydrophobic silica in the total silica covering the urethane beads is not particularly limited as long as it is 20% by mass or more, but the water absorption rate of the photosensitive resin composition can be further reduced, and the insulation reliability is further excellent. From the viewpoint of forming a cured film, 30% by mass or more is preferable, 40% by mass or more is more preferable, and 60% by mass or more is particularly preferable.
  • the upper limit of the ratio of hydrophobic silica to the total silica covering the urethane beads is preferably as high as possible, and examples thereof include 100% by mass.
  • the ratio of hydrophobic silica to the total silica covering the urethane beads is 100% by mass, that is, the silica coating the urethane beads is made of hydrophobic silica, so that the water absorption rate of the photosensitive resin composition is further ensured. It is possible to form a cured film with further improved insulation reliability.
  • silica other than hydrophobic silica that can be used for silica that coats urethane beads include untreated silica that has not been surface-treated, that is, hydrophilic silica.
  • the coverage of all silica including hydrophobic silica of urethane beads is not particularly limited, but the lower limit thereof is from the point that a photosensitive resin composition having excellent dispersibility during storage and storage can be obtained more reliably. , 1.0% by mass is preferable, 5.0% by mass is more preferable, and 8.0% by mass is further preferable, from the viewpoint that a photosensitive resin composition having excellent dispersibility during storage and storage can be obtained more reliably. , 12% by mass is particularly preferable.
  • the upper limit of the coverage of all silica of the urethane beads is preferably 40% by mass, more reliably, from the viewpoint that a photosensitive resin composition capable of more reliably forming a cured film having excellent bendability can be obtained. 30% by mass is more preferable, 25% by mass is further preferable, and 18% by mass is particularly preferable, from the viewpoint that a photosensitive resin composition capable of forming a cured film having excellent bendability can be obtained.
  • the hydrophobic silica is not particularly limited as long as it is a silica having a hydrophobic substituent, but for example, a photosensitive resin composition capable of more reliably reducing the water absorption rate while having excellent dispersibility during storage and storage.
  • Alkylsiloxylated silica dialkylsiloxylated silica surface-modified with a dialkylsilyl group, trialkylsiloxylated silica surface-modified with a trialkylsilyl group, and surface-modified with a (meth) acrylicsilyl group.
  • Preferables are (meth) acrylic siloxylated silica, silica surface-modified with a dialkylsiloxane group, silica surface-modified with a dialkylpolysiloxane group, and the like.
  • a photosensitive resin composition capable of reducing the water absorption rate while having excellent dispersibility during storage and storage can be obtained more reliably, and a cured film having excellent bendability and insulation reliability can be obtained more reliably.
  • Monoalkyl siroxylated silica surface-modified with a monoalkylsilyl group, dialkylsiloxylated silica surface-modified with a dialkylsilyl group from the viewpoint that a photosensitive resin composition capable of forming the above can be obtained.
  • Particularly preferred is (meth) acrylic siloxylated silica, which has been surface modified with a (meth) acrylic silyl group.
  • the carbon number of each of the above-mentioned dialkyl and trialkyl is not particularly limited, but is preferably 1 or more and 10 or less, more preferably 1 or more and 5 or less, and 1 or more and 3 or less. Especially preferable.
  • the carbon number of the monoalkyl described above is not particularly limited, but is preferably 1 or more and 20 or less, more preferably 3 or more and 15 or less, and particularly preferably 5 or more and 10 or less.
  • hydrophobic silica may be used alone or in combination of two or more.
  • the content of the urethane beads coated with silica is not particularly limited, but for example, the lower limit thereof more reliably obtains a photosensitive resin composition capable of reducing water absorption while having excellent dispersibility during storage and storage. From the viewpoint that a photosensitive resin composition capable of forming a cured film having excellent bendability and insulation reliability can be obtained more reliably, with respect to 100 parts by mass of the carboxyl group-containing photosensitive resin. 35 parts by mass is preferable, 50 parts by mass is more preferable, and 60 parts by mass is particularly preferable.
  • the upper limit of the content of the urethane beads coated with silica is 150 mass by mass with respect to 100 parts by mass of the carboxyl group-containing photosensitive resin from the viewpoint of imparting excellent coatability to the photosensitive resin composition. Parts are preferable, 120 parts by mass is more preferable, and 90 parts by mass is particularly preferable.
  • the average particle size of the urethane beads coated with silica is not particularly limited, but for example, the urethane beads are surely coated with silica containing hydrophobic silica to ensure the dispersibility and insulation reliability of the photosensitive resin composition. It is preferably 1.0 ⁇ m or more and 10 ⁇ m or less, more preferably 2.0 ⁇ m or more and 7.0 ⁇ m or less, and more preferably 3.0 ⁇ m, from the viewpoint of uniformly dispersing urethane beads coated with silica in the photosensitive resin composition. More than 5.0 ⁇ m or less is particularly preferable.
  • the photopolymerization initiator of the component (D) is not particularly limited, and is, for example, 1,2-octanedione, 1- [4- (phenylthio) -2- (O-benzoyloxime)], etanone 1- [9-].
  • Examples of the photopolymerization initiator other than the oxime ester-based photopolymerization initiator and the ⁇ -aminoalkylphenone-based photopolymerization initiator include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin-n-butyl ether.
  • Benzophenone such as benzoin isobutyl ether; acetophenone, dimethylaminoacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone and other acetophenone; benzophenone, p-phenylbenzophenone, 4, Benzophenone series such as 4'-diethylaminobenzophenone and dichlorobenzophenone; anthraquinone series such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-tertiary butyl anthraquinone and 2-aminoanthraquinone; 2-methylthioxanthone, 2-ethylthioxanthone, Thioxanthone series such as 2-chlorthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone; benzyldimethylketal
  • the content of the photopolymerization initiator is not particularly limited, but is preferably 0.1 part by mass or more and 10 parts by mass or less, and 0.2 parts by mass or more and 5.0 parts by mass with respect to 100 parts by mass of the carboxyl group-containing photosensitive resin. Part or less is particularly preferable.
  • the reactive diluent of the component (E) is, for example, a photopolymerizable monomer, which is a compound having at least one polymerizable double bond per molecule, preferably two or more polymerizable double bonds per molecule.
  • the reactive diluent reinforces the photocuring of the photosensitive resin composition and contributes to imparting sufficient heat resistance, acid resistance, alkali resistance and the like to the cured product of the photosensitive resin composition.
  • Examples of the reactive diluent include monofunctional (meth) acrylate compounds, bifunctional (meth) acrylate compounds, trifunctional (meth) acrylate compounds, and tetrafunctional or higher (meth) acrylate compounds. ..
  • Examples of the (meth) acrylate compound include 2-hydroxyethyl (meth) acrylate, phenoxyethyl (meth) acrylate, diethylene glucol mono (meth) acrylate, and 2-hydroxy-3-phenoxypropyl (meth) acrylic rate.
  • Monofunctional (meth) acrylate compounds 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, neo Pentyl glycol adipate di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, ethylene oxide-modified di (meth) acrylate, allylated cyclohexyl di (meth) acrylate, Bifunctional (meth) acrylate compounds such as isocyanurate di (meth) acrylate; trimethylol propanetri (meth) acrylate, dipentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, propy
  • Trifunctional (meth) acrylate compounds such as (meth) acrylate, tris (acryloxyethyl) isocyanurate; ditrimethylolpropanetetra (meth) acrylate, propionic acid-modified dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth).
  • Examples thereof include tetrafunctional or higher functional (meth) acrylate compounds such as acrylate.
  • a monofunctional or bifunctional or higher urethane (meth) acrylate compound and the like can be mentioned. These may be used alone or in combination of two or more.
  • the content of the reactive diluent is not particularly limited, but is preferably 5.0 parts by mass or more and 50 parts by mass or less, and particularly 10 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the carboxyl group-containing photosensitive resin. preferable.
  • the photosensitive resin composition of the present invention in addition to the above-mentioned components (A) to (E), various components such as extender pigments, curing accelerators, various additives, flame retardants, and coloring are required. Agents, non-reactive diluents and the like can be blended.
  • Examples of the extender pigment include talc, barium sulfate, alumina, aluminum hydroxide, mica and the like.
  • Examples of the curing accelerator include boron trifluoride-amine complex, dicyandiamide (DICY) and its derivatives, organic acid hydrazide, diaminomaleonitrile (DAMN) and its derivatives, guanamine and its derivatives, melamine and its derivatives, and amineimide ( AI) and polyamines can be mentioned.
  • Examples of various additives include defoaming agents such as silicone-based, hydrocarbon-based and acrylic-based, organic fillers such as (meth) acrylic polymers and organic bentonite, and thixotropic agents such as polycarboxylic acid amide. Can be mentioned.
  • Examples of the flame retardant include phosphorus-based flame retardants.
  • Examples of the phosphorus-based flame retardant include tris (chloroethyl) phosphate, tris (2,3-dichloropropyl) phosphate, tris (2-chloropropyl) phosphate, tris (2,3-bromopropyl) phosphate, and tris (bromo).
  • Halogen-containing phosphoric acid such as chloropropyl) phosphate, 2,3-dibromopropyl-2,3-chloropropyl phosphate, tris (tribromophenyl) phosphate, tris (dibromophenyl) phosphate, tris (tribromoneopentyl) phosphate, etc.
  • Non-halogen aliphatic phosphates such as trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate; triphenyl phosphate, cresyldiphenyl phosphate, dicresylphenyl phosphate, tricresyl phosphate, trixylate Nylphosphate, xylenyldiphenyl phosphate, tris (isopropylphenyl) phosphate, isopropylphenyldiphenyl phosphate, diisopropylphenylphenyl phosphate, tris (trimethylphenyl) phosphate, tris (t-butylphenyl) phosphate, hydroxyphenyldiphenyl phosphate, octyldiphenyl phosphate.
  • Non-halogen aromatic phosphate esters such as: Aluminum Trisdiethylphosphine, Aluminum Trismethylethylphosphine, Aluminum Trisdiphenylphosphine, Zinc bisdiphenylphosphine, Zinc bismethylethylphosphine, Zinc bisdiphenylphosphine, Bisdiethyl Metal salts of phosphinic acids such as titanyl phosphinate, titanium tetrakisdiethylphosphine, titanyl bismethylethylphosphine, titanium tetrakismethylethylphosphine, titanyl bisdiphenylphosphine, titanium tetrakisdiphenylphosphine, diphenylvinylphosphine oxide, triphenyl Examples thereof include phosphine oxide compounds such as phosphine oxide, trialkylphosphine oxide, and tris (hydroxyalkyl) phosphine oxide. Of these, organic
  • the colorant is not particularly limited, such as pigments and pigments. Further, as the color of the colorant, any colorant such as a white colorant, a blue colorant, a green colorant, a yellow colorant, an orange colorant, a red colorant, a purple colorant, and a black colorant can be used. Is.
  • the inorganic colorant include titanium oxide, which is a white colorant, carbon black, which is a black colorant, and acetylene black, which are black colorants.
  • organic colorant examples include phthalocyanine green which is a green colorant, phthalocyanine type such as phthalocyanine blue and lionol blue which are blue colorants, and diketopyrrolopyrrole type such as chromoftalo orange which is an orange colorant. And so on.
  • the non-reactive diluent is a component for adjusting the viscosity, coatability, drying property, etc. of the photosensitive resin composition.
  • the non-reactive diluent include organic solvents.
  • the organic solvent include ketones such as methyl ethyl ketone, aromatic hydrocarbons such as toluene and xylene, alcohols such as methanol, n-propanol, isopropanol, cyclohexanol and propylene glycol monomethyl ether, cyclohexane and methylcyclohexane.
  • Alicyclic hydrocarbons such as cellosolve and butyl cellosolve
  • carbitols such as carbitol and butyl carbitol
  • ethyl acetate butyl acetate
  • cellosolve acetate butyl cellosolve acetate
  • carbitol acetate carbitol acetate
  • diethylene glycol monomethyl examples thereof include esters such as ether acetate, ethyl diglycol acetate, and propylene glycol monomethyl ether acetate.
  • the content of the non-reactive diluent is not particularly limited, but is preferably 2.0 parts by mass or more and 50 parts by mass or less, and 5.0 parts by mass or more and 20 parts by mass with respect to 100 parts by mass of the carboxyl group-containing photosensitive resin. The following are particularly preferred.
  • the method for producing the photosensitive resin composition of the present invention is not limited to a specific method, and a known method can be used. Specifically, for example, after blending each of the above components in a predetermined ratio, at room temperature (for example, 25 ° C.), a kneading means such as a three-roll, ball mill, sand mill, bead mill, kneader, or a super mixer or planetary mixer. , Trimix and the like can be kneaded or mixed and produced. Further, before the kneading or mixing, pre-kneading or pre-mixing may be carried out, if necessary.
  • a kneading means such as a three-roll, ball mill, sand mill, bead mill, kneader, or a super mixer or planetary mixer. , Trimix and the like can be kneaded or mixed and produced. Further, before the kneading or mixing, pre-k
  • an insulating protective film for example, a solder resist film
  • a dry film coated with the photosensitive resin composition of the present invention on a printed wiring board having a circuit pattern formed by etching a conductor such as a copper foil. Etc. will be described as an example.
  • the dry film includes a support film (for example, a thermoplastic resin film such as a polyethylene terephthalate film or a polyester film), a solder resist layer coated on the support film, and a cover film (for example, polyethylene) that protects the solder resist layer. It has a laminated structure with a film (film, polypropylene film).
  • the photosensitive resin composition of the present invention is applied onto a support film by a known method such as a roller coating method or a bar coater method to form a coating film having a predetermined film thickness.
  • a solder resist layer is formed on the support film by drying the coating film of the formed photosensitive resin composition. Then, by laminating a cover film on the formed solder resist layer, a dry film having a coating film of the photosensitive resin composition of the present invention can be produced.
  • the solder resist layer is formed on the printed wiring board by laminating the solder resist layer and the printed wiring board such as the flexible printed wiring board while peeling off the cover film.
  • the support film is still laminated on the solder resist layer.
  • pre-drying is performed by heating at a temperature of about 60 to 100 ° C. for about 5 to 30 minutes in order to volatilize the non-reactive diluent (organic solvent) in the photosensitive resin composition, and then solder resist. Make the surface of the layer tack-free.
  • a negative film (photomask) having a translucent pattern other than the land of the circuit pattern is placed on the support film, and ultraviolet rays (for example, a wavelength range of 300 to 400 nm) are irradiated from above the negative film.
  • the solder resist layer is photocured.
  • the support film is peeled off, and the non-exposed region corresponding to the land is removed with a dilute alkaline aqueous solution to develop the solder resist layer.
  • a spray method, a shower method or the like is used, and examples of the dilute alkaline aqueous solution used include a 0.5 to 5% by mass sodium carbonate aqueous solution.
  • the solder resist layer is thermoset (post-cured) for 20 to 80 minutes in a hot air circulation type dryer or the like at 130 to 170 ° C., so that the solder is a photocurable film on the printed wiring board.
  • a resist film can be formed.
  • a method of applying the photosensitive resin composition of the present invention to a printed wiring board to form an insulating protective film for example, a solder resist film
  • an insulating protective film for example, a solder resist film
  • the photosensitive resin composition of the present invention is applied onto a printed wiring board such as a flexible printed wiring board by a screen printing method, a bar coater method, an applicator method, a blade coater method, a knife coater method, a roll coater method, a gravure coater method, and a spray coater.
  • a coating film is formed by applying to a desired thickness by a known method such as a method. Then, if necessary, pre-drying is performed by heating at a temperature of about 60 to 100 ° C. for about 5 to 30 minutes in order to volatilize the non-reactive diluent (organic solvent) in the photosensitive resin composition. To be tack-free.
  • a negative film (photomask) having a pattern having a translucent pattern other than the land of the circuit pattern is adhered to the coating film, and ultraviolet rays (for example, a wavelength range of 300 to 400 nm) are irradiated from above the negative film (photomask) to apply the coating film. Photocure the film. Then, the non-exposed region corresponding to the land is removed with a dilute alkaline aqueous solution to develop the coating film.
  • a spray method, a shower method or the like examples of the dilute alkaline aqueous solution to be used include a 0.5 to 5% by mass sodium carbonate aqueous solution.
  • solder resist film which is a photocurable film
  • a solder resist film is formed on the printed wiring board by heat curing treatment (post-cure) for 20 to 80 minutes in a hot air circulation type dryer or the like at 130 to 170 ° C. Can be made to.
  • Urethane beads / Urethane beads A As hydrophobic silica, 10 g of dimethylsiloxylated silica (trade name "Aerosil R974", Nippon Aerosil Co., Ltd., average primary particle diameter 0.012 ⁇ m) is uniformly dispersed in 100 g of a solvent. Urethane beads A (average particles) having a silica coverage of 10% by mass by uniformly dispersing an emulsion containing polyurethane spheres obtained by reacting 20 g of an isocyanate compound with 20 g of alcohols with a homogenizer and then drying the mixture. Diameter 3 ⁇ m) was prepared.
  • the silica coverage was determined from the ash content after complete combustion at 600 ° C. for 2 hours.
  • Urethane beads B Urethane beads B (average particle diameter 3 ⁇ m) having a silica coverage of 15% by mass were prepared in the same manner as urethane beads A.
  • Urethane beads C In the same manner as urethane beads A, urethane beads C (average particle diameter 3 ⁇ m) having a silica coverage of 20% by mass were prepared.
  • urethane beads D With urethane beads A, except that octylsiloxylated silica (trade name "Aerosil R805", Nippon Aerosil Co., Ltd., average primary particle diameter 0.012 ⁇ m) was used instead of dimethylsiloxylated silica. Similarly, urethane beads D (average particle diameter 3 ⁇ m) having a silica coverage of 15% by mass were prepared.
  • urethane beads E With urethane beads A, except that methacrylicylated silica (trade name "Aerosil R711", Nippon Aerosil Co., Ltd., average primary particle diameter 0.012 ⁇ m) was used instead of dimethylsiloxylated silica. Similarly, urethane beads E (average particle diameter 3 ⁇ m) having a silica coverage of 15% by mass were prepared.
  • methacrylicylated silica trade name "Aerosil R711", Nippon Aerosil Co., Ltd., average primary particle diameter 0.012 ⁇ m
  • Urethane beads F Dimethylsiloxylated silica and untreated silica (trade name "Aerosil 200", Nippon Aerosil Co., Ltd., average primary particle diameter 0.012 ⁇ m) used in Urethane beads A are used in a mass ratio of 1: 1.
  • Urethane beads F (average particle diameter 3 ⁇ m) having a coverage of 15% by mass of silica (hydrophobic silica 50% by mass) were prepared in the same manner as the urethane beads A.
  • Urethane beads G Silica (hydrophobic silica 33% by mass) in the same manner as urethane beads A, except that the dimethylsiloxylated silica used in urethane beads A and untreated silica were used in a mass ratio of 1: 2. Urethane beads G (average particle diameter 3 ⁇ m) having a coverage of 15% by mass were prepared. Urethane beads H: Silica (hydrophobic silica 25% by mass) in the same manner as urethane beads A, except that the dimethylsiloxylated silica used in urethane beads A and untreated silica were used in a mass ratio of 1: 3. Urethane beads H (average particle diameter 3 ⁇ m) having a coverage of 15% by mass were prepared.
  • Urethane beads I Urethane beads I (average particle diameter 3 ⁇ m) having a silica coverage of 10% by mass were prepared in the same manner as urethane beads A except that the untreated silica used in the preparation of urethane beads F was used. ..
  • Urethane beads J Urethane beads J (average particle diameter 3 ⁇ m) having a silica coverage of 15% by mass were prepared in the same manner as urethane beads A except that the untreated silica used in the preparation of urethane beads F was used. ..
  • Urethane beads K Urethane beads K (average particle diameter 3 ⁇ m) having a silica coverage of 20% by mass were prepared in the same manner as urethane beads A except that the untreated silica used in the preparation of urethane beads F was used. ..
  • Hajilite H42M Showa Denko Corporation Flame Retardant / Exorit OP-935: Clariant Japan Co., Ltd.
  • Hardening Accelerator / Melamine Nissan Chemical Corporation / DICY-7: Mitsubishi Chemical Corporation Additive / AC-303: Organic System filler, Shin-Etsu Chemical Co., Ltd.
  • Specimen manufacturing process Board Flexible printed wiring board (polyimide film, Panasonic Corporation, film thickness 25 ⁇ m, conductor (Cu foil) thickness 12.5 ⁇ m)
  • Surface treatment 5% by mass sulfuric acid aqueous solution
  • Coating Screen printing Pre-drying: 80 ° C in a BOX furnace, 20 minutes exposure: 100 mJ / cm 2 on a photosensitive resin composition (main wavelength 365 nm, direct drawing by Oak Co., Ltd.
  • the evaluation items are as follows. (1) Dispersibility (blocking) 200 g of the photosensitive resin composition was placed in a 300 ml plastic container, sealed, and left in a heat insulating tank at 30 ° C. for 72 hours, and the state was visually observed and evaluated according to the following criteria. The viscosity of the photosensitive resin composition was measured with a Brookfield B-type viscometer. ⁇ : The viscosity of the photosensitive resin composition after being left to stand has a rate of change of 10% or less with respect to the initial value, and no aggregated particles (blocking) are observed.
  • ⁇ The viscosity of the photosensitive resin composition after being left to stand has a rate of change of more than 10% and 20% or less with respect to the initial value, and no aggregated particles (blocking) are observed.
  • ⁇ The viscosity of the photosensitive resin composition after being left to stand has a rate of change of more than 20% and 30% or less with respect to the initial value, and no aggregated particles (blocking) are observed.
  • X The change rate of the viscosity of the photosensitive resin composition after standing by more than 30% with respect to the initial value, or agglomerated particles (blocking) are observed in the photosensitive resin composition.
  • Insulation reliability (insulation reliability in the thickness direction (Z-axis direction) of the coating film)
  • the top surface of the electromagnetic wave shield film (Tatsuta Electric Wire Co., Ltd., "SF-PC5000”) pasted on the cured coating film is used as the anode, and copper, which is the conductor of the test piece, is used.
  • SF-PC5000 electromagnetic wave shield film
  • 50 V was applied in a constant temperature and humidity chamber at 60 ° C. and a humidity of 95%, and the resistance value was continuously measured using an ion migration tester (IMV, “MIG-8600B / 128”).
  • the measurement start time is when 50 V is applied, the time until the resistance value drops to less than 1.0E + 6 (1.0 ⁇ 106) ⁇ is measured, and this is the dielectric breakdown time.
  • the insulation breakdown in the Z-axis direction) was evaluated.
  • ⁇ Dielectric breakdown time 1500 hours or more.
  • ⁇ Dielectric breakdown time 1000 hours or more and less than 1500 hours.
  • ⁇ Dielectric breakdown time 500 hours or more and less than 1000 hours.
  • X Dielectric breakdown time is less than 500 hours.
  • the photosensitive resin compositions of Examples 1 to 8 even after being left for 72 hours. It was possible to form a cured film having excellent dispersibility, a reduced water absorption rate, and excellent bendability and insulation reliability.
  • Examples 1 to 5 in which the silica covering the urethane beads is entirely hydrophobic silica have water absorption as compared with Examples 6 to 8 in which the ratio of hydrophobic silica in the total silica is 25 to 50% by mass. The rate was further reduced and the insulation reliability was further improved. Further, in Example 2 in which the silica coverage is 15% by mass, the dispersibility is further improved as compared with Example 1 in which the silica coverage is 10% by mass, and the silica coverage is 20% by mass. The bendability was further improved as compared with a certain Example 3.
  • Example 2 in which the urethane beads were coated with dimethylsiloxylated silica was compared with Example 4 in which the urethane beads were coated with octylsiloxylated silica and Example 5 in which the urethane beads were coated with methacrylicylated silica.
  • Example 4 in which the urethane beads were coated with octylsiloxylated silica was compared with Example 4 in which the urethane beads were coated with octylsiloxylated silica
  • Example 5 in which the urethane beads were coated with methacrylicylated silica.
  • the water absorption rate could be reduced as the ratio of hydrophobic silica in the total silica increased.
  • Comparative Example 1 in which urethane beads were not blended, bendability could not be obtained. Further, in Comparative Example 2 in which hydrophobic silica was not blended and the silica coverage was 10% by mass, dispersibility could not be obtained and the water absorption rate was high. In Comparative Example 3 in which hydrophobic silica is not blended and the silica coverage is 15% by mass, and in Comparative Example 4 in which hydrophobic silica is not blended and the silica coverage is 20% by mass, water absorption is absorbed. The rate was high and insulation reliability could not be obtained.
  • a cured film having excellent dispersibility during storage and storage, reducing the water absorption rate, and having excellent bendability and insulation reliability. Therefore, for example, insulation of a solder resist film or the like on a flexible printed wiring board can be formed. It has high utility value in the field of providing a protective film.

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Materials For Photolithography (AREA)
  • Non-Metallic Protective Coatings For Printed Circuits (AREA)

Abstract

La présente invention concerne une composition de résine photosensible qui présente une excellente dispersibilité pendant l'entreposage et la conservation, qui est capable de réduire le coefficient d'absorption d'eau, et qui est capable de former un film durci ayant une excellente aptitude au pliage et une excellente fiabilité d'isolation.　La composition de résine photosensible comprend (A) une résine photosensible contenant des groupes carboxyles, (B) un composé époxy, (C) des billes d'uréthane, (D) un initiateur de photopolymérisation et (E) un diluant réactif. Les billes d'uréthane (C) sont revêtues de silice, et au moins 20 % en masse de 100 % en masse de la silice est de la silice hydrophobe.
PCT/JP2021/043588 2020-11-30 2021-11-29 Composition de résine photosensible WO2022114175A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002293882A (ja) * 2001-03-30 2002-10-09 Taiyo Ink Mfg Ltd 光硬化性・熱硬化性樹脂組成物及びプリント配線板
JP2019056824A (ja) * 2017-09-21 2019-04-11 株式会社タムラ製作所 感光性樹脂組成物の光硬化膜及び感光性樹脂組成物の光硬化膜を有するプリント配線板
JP2020148971A (ja) * 2019-03-14 2020-09-17 株式会社タムラ製作所 感光性樹脂組成物

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002293882A (ja) * 2001-03-30 2002-10-09 Taiyo Ink Mfg Ltd 光硬化性・熱硬化性樹脂組成物及びプリント配線板
JP2019056824A (ja) * 2017-09-21 2019-04-11 株式会社タムラ製作所 感光性樹脂組成物の光硬化膜及び感光性樹脂組成物の光硬化膜を有するプリント配線板
JP2020148971A (ja) * 2019-03-14 2020-09-17 株式会社タムラ製作所 感光性樹脂組成物

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