WO2017170050A1 - Encre de réserve, produit durci de celle-ci, film protecteur pour lignes de câblage et procédé de production d'un film protecteur pour lignes de câblage - Google Patents

Encre de réserve, produit durci de celle-ci, film protecteur pour lignes de câblage et procédé de production d'un film protecteur pour lignes de câblage Download PDF

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Publication number
WO2017170050A1
WO2017170050A1 PCT/JP2017/011481 JP2017011481W WO2017170050A1 WO 2017170050 A1 WO2017170050 A1 WO 2017170050A1 JP 2017011481 W JP2017011481 W JP 2017011481W WO 2017170050 A1 WO2017170050 A1 WO 2017170050A1
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Prior art keywords
meth
resist ink
compound
group
containing compound
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English (en)
Japanese (ja)
Inventor
一彦 大賀
大西　美奈
快 鈴木
明子 佐藤
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Resonac Holdings Corp
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Showa Denko KK
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Priority to JP2018509131A priority Critical patent/JPWO2017170050A1/ja
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/02—Polythioethers
    • C08G75/04—Polythioethers from mercapto compounds or metallic derivatives thereof
    • C08G75/045—Polythioethers from mercapto compounds or metallic derivatives thereof from mercapto compounds and unsaturated compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
    • 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 relates to a resist ink, a cured product thereof, a protective film for wiring, and a manufacturing method thereof.
  • Patent Documents 1 to 3 disclose resist inks that can form resists having acid resistance, but have not been sufficiently resistant to strongly acidic electroless tin plating solutions.
  • an object of the present invention is to provide a resist ink that can solve the above-described problems of the prior art and can form a cured product having excellent acid resistance.
  • Another object of the present invention is to provide a cured product having excellent acid resistance. Furthermore, this invention makes it a subject to provide the protective film of the wiring excellent in acid resistance, and its manufacturing method.
  • the (meth) allyl group-containing compound (A) includes diallyl phthalate, diallyl isophthalate, diallyl terephthalate, diallyl 1,4-cyclohexanedicarboxylate, diallyl 1,3-cyclohexanedicarboxylate, 1,2-
  • the resist ink according to [1] comprising at least one selected from diallyl cyclohexanedicarboxylate and triallyl isocyanurate.
  • the resist ink according to any one of [1] to [5], wherein the thiol compound (B) includes a compound having two or more secondary or tertiary mercapto groups in one molecule.
  • the thiol compound (B) is 1,4-bis (3-mercaptobutyryloxy) butane, pentaerythritol tetrakis (3-mercaptobutyrate), 1,3,5-tris (3-mercaptobutyryl).
  • the (meth) acryloyl group-containing compound (D) is selected from epoxy (meth) acrylate, (poly) ester (meth) acrylate, (poly) carbonate (meth) acrylate, and hydrogenated polybutadiene (meth) acrylate.
  • the compound (D) according to any one of [8] to [10], wherein the (meth) acryloyl group-containing compound (D) includes a compound having at least one structure selected from an alicyclic structure and an aromatic ring structure. Resist ink. [12] The ratio of the number of (meth) allyl groups in the (meth) allyl group-containing compound (A) to the number of mercapto groups in the thiol compound (B) (number of allyl groups / number of mercapto groups) is 0.
  • Content of the polymerization initiator (C) when the total content of the (meth) allyl group-containing compound (A), the thiol compound (B), and the (meth) acryloyl group-containing compound (D) is 100 parts by mass.
  • the resist ink film is irradiated with active energy rays having a wavelength that generates a polymerizable radical species in the polymerization initiator (C) on a part or all of the region including the region covering the wiring in the resist ink film.
  • a cured product excellent in acid resistance and a protective film for wiring can be provided.
  • the resist ink of this embodiment includes a (meth) allyl group-containing compound (A) having two or more (meth) allyl groups in one molecule, and a thiol compound having two or more mercapto groups in one molecule ( B) and a polymerization initiator (C).
  • the resist ink of this embodiment can be easily cured in a short time by irradiation with active energy rays or heat, and the cured product has excellent acid resistance. Therefore, the resist ink of this embodiment can be used suitably as a protective material for acidic liquid protection.
  • the cured product of the resist ink of the present embodiment is sufficiently resistant to an acidic plating solution. Therefore, when plating a copper wiring used for a printed wiring board or the like with an acidic plating solution, the resist (wiring of the wiring) is used. It can be used as a protective film.
  • the electroless tin plating solution used for tin plating is particularly strongly acidic
  • the cured product of the resist ink of this embodiment has resistance, so tin plating is performed using the electroless tin plating solution. It can also be used as a resist.
  • the cured product of the resist ink (wiring protective film) of the present embodiment has excellent adhesion to the substrate to be coated, as well as excellent moisture resistance and heat resistance, and has a long-term insulation at a high level. It also has reliability. Furthermore, the resist ink of the present embodiment does not need to be dissolved in a solvent and can be made solvent-free, so that it is difficult to cause environmental pollution.
  • the “(meth) acryloyl group” in the present specification means an acryloyl group and / or a methacryloyl group.
  • “(meth) allyl” means methallyl (ie, 2-methyl-2-propenyl) and / or allyl (ie, 2-propenyl).
  • (meth) acrylate” means methacrylate and / or acrylate, and “(meth) acryl” means methacryl and / or acrylic.
  • the (meth) allyl group-containing compound (A) is a compound having two or more (meth) allyl groups in one molecule, and may be a monomer, an oligomer or a polymer, From the viewpoint, a compound having a number average molecular weight of 200 or more and 20000 or less is preferable.
  • the molecular weight of the oligomer or polymer in this invention is the number average molecular weight of polystyrene (PS) conversion measured by the gel permeation chromatography method (GPC method). Detailed measurement conditions of the molecular weight are shown in the examples described later.
  • Examples of the (meth) allyl group-containing compound (A) include a compound (a-1) having at least one structure selected from an alicyclic structure, an aromatic ring structure, and a heterocyclic structure in the molecule and an acyclic compound ( a-2).
  • Examples of the alicyclic structure include alicyclic rings having 3 to 6 carbon atoms, preferably a cyclohexane ring and a cycloheptane ring.
  • Examples of the aromatic ring structure include aromatic rings having 6 to 10 carbon atoms, preferably a benzene ring and a naphthalene ring.
  • heterocyclic structure examples include a three-membered ring to a ten-membered ring having a nitrogen atom, an oxygen atom, or a sulfur atom, and examples thereof include a pyridine ring, a triazine ring, a ring derived from cyanuric acid, and a ring derived from isocyanuric acid.
  • examples of the compound (a-1) include diallyl phthalate, diallyl isophthalate, diallyl terephthalate, triallyl trimellitic acid, and tetraallyl pyromellitic acid.
  • Allyloxycarbonyl group-containing compounds having an aromatic ring structure diallyl 1,2-cyclohexanedicarboxylate, diallyl 1,3-cyclohexanedicarboxylate, diallyl 1,4-cyclohexanedicarboxylate, triallyl 1,2,4-cyclohexanetricarboxylate 1,2,4,5-cyclohexanetetracarboxylic acid tetraallyl, 5-alkyl-substituted cyclohexane-1,4-dicarboxylic acid diallyl, 5-halogen-substituted cyclohexane-1,4-dicarboxylic acid diallyl, 1,3-adamantane dicarboxylic acid Diallyl 1,3,5-adamantanetricarboxylic acid triallyl, hydrogenated bisphenol A type diallyl ether, hydrogenated dimer acid (having 36 or 44 carbon atoms and having an alicyclic structure) diallyl, tricyclodecan
  • Examples of the compound (a-1) include a metalyloxycarbonyl group-containing compound having an aromatic ring structure such as dimethallyl phthalate, dimethallyl isophthalate, dimethallyl terephthalate, trimethallyl trimellitic acid, tetramethallyl pyromellitic acid, -Dimethallyl cyclohexanedicarboxylate, dimethallyl 1,3-cyclohexanedicarboxylate, dimethallyl 1,4-cyclohexanedicarboxylate, trimethallyl 1,2,4-cyclohexanetricarboxylate, tetramethallyl 1,2,4,5-cyclohexanetetracarboxylate, 5 -Alkyl-substituted cyclohexane-1,4-dicarboxylate dimethallyl, 5-halogen-substituted cyclohexane-1,4-dicarboxylate dime
  • compound (a-1) bisphenol A diallyl ether, bisphenol A dimethallyl ether, bisphenol S diallyl ether, bisphenol S dimethallyl ether, 1,4-naphthalenedicarboxylic acid diallyl ether, 1,4-naphthalenedicarboxylic acid Dimethallyl ether, 1,5-naphthalenedicarboxylic acid diallyl ether, 1,5-naphthalenedicarboxylic acid dimethallyl ether, 2,6-naphthalenedicarboxylic acid diallyl ether, 2,6-naphthalenedicarboxylic acid dimethallyl ether, 2,7- Naphthalenedicarboxylic acid diallyl ether, 2,7-naphthalenedicarboxylic acid dimethallyl ether, diphenyl-m, m′-dicarboxylic acid diallyl ether, diphenyl-m, m′-dimethallyl ether Diphenyl-p, p
  • Compound (a-1) includes allyl methallyl phthalate, allyl methallyl isophthalate, diallyl methallyl trimellitic acid, allyl dimethallyl trimellitic acid, triallyl methallyl pyromellitic acid, diallyl dimetall pyromellitic acid Ester, pyromellitic acid allyltrimethallyl ester, bisphenol A allylmethallyl ether, bisphenol S allylmethallyl ether, 1,4-naphthalenedicarboxylic acid allylmethallyl ether, 1,5-naphthalenedicarboxylic acid allylmethallyl ether, 2,6-naphthalenedicarboxylic acid Acid allylmethallyl ether, 2,7-naphthalenedicarboxylic acid allylmethallyl ether, diphenyl-m
  • the compound (a-1) is more preferable than the compound (a-2).
  • the compound (a-2) is more preferable than the compound (a-2).
  • the compound (a-2) is more preferable than the compound (a-2).
  • the compound (a-2) is more preferable than the compound (a-2).
  • the compound (a-2) is more preferable than the compound (a-2).
  • the compound (A) is a monomer and when the (meth) allyl group-containing compound (A) described later is an oligomer.
  • compounds having at least one of an allyloxycarbonyl group and an N-allyl group are preferable.
  • the compound (a-1) having at least one of an allyloxycarbonyl group and an N-allyl group Preferred are diallyl phthalate, diallyl isophthalate, diallyl terephthalate, diallyl 1,4-cyclohexanedicarboxylate, diallyl 1,3-cyclohexanedicarboxylate, diallyl 1,2-cyclohexanedicarboxylate, and triallyl isocyanurate. .
  • examples of the (meth) allyl group-containing compound (A) include (meth) allyl ester resins.
  • the (meth) allyl ester resin is a compound having a (meth) allyloxycarbonyl group at the molecular end and a repeating unit in the molecule.
  • transesterification reaction between a polybasic acid (meth) allyl ester compound and a polyhydric alcohol an alcohol such as a monool or polyhydric alcohol containing (meth) allyl allyl alcohol, a polybasic acid and a polybasic acid anhydride
  • Condensation reaction with at least one selected from the above a transesterification reaction between a polyol having a repeating unit and a (meth) allyl ester compound of a polybasic acid, a monool containing (meth) allylallyl alcohol, a polyol having a repeating unit, etc.
  • an organometallic compound is particularly preferable, and specific examples include tetraisopropoxy titanium, tetra-n-butoxy titanium, dibutyl tin oxide, dioctyl tin oxide, acetylacetone hafnium, acetylacetone zirconium and the like. be able to.
  • the reaction temperature for the transesterification reaction is preferably 100 ° C. or higher and 230 ° C. or lower, more preferably 120 ° C. or higher and 200 ° C. or lower.
  • the boiling point may limit.
  • the polyhydric alcohol used may be limited.
  • a solvent that does not inhibit the transesterification reaction it is not necessary to use a solvent, but if necessary, a solvent that does not inhibit the transesterification reaction can also be used.
  • Specific examples include benzene, toluene, xylene, cyclohexane and the like. Of these, benzene and toluene are preferred.
  • Specific examples of the (meth) allyl ester resin include, for example, oligomers having a structure represented by the following formulas (1), (2), and (4).
  • R 1 s in the formula (1) each independently represent a linear alkylene group or a branched alkylene group having 1 to 36 carbon atoms (preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms).
  • R 2 and R 3 each independently represent a hydrogen atom or a methyl group. Preferably, both R 2 and R 3 are hydrogen atoms.
  • Xs are each independently an organic group derived from a divalent carboxylic acid, preferably having an alkyl group having 1 to 4 carbon atoms as a substituent. It may be a phenylene group or a cyclohexylene group, more preferably a phenylene group or a cyclohexylene group having no substituent.
  • alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, and a tert-butyl group.
  • the position at which the phenylene group or cyclohexylene group is bonded to the adjacent carbonyl carbon may be any of the 1,2-position, 1,3-position, and 1,4-position, but considering the ease of synthesis, the 1,3-position or 1-position , 4th position is preferred.
  • N in Formula (1) is an integer of 1 or more and 20 or less, preferably 1 or more and 18 or less, and more preferably 1 or more and 15 or less.
  • the molecular weight of the oligomer represented by the formula (1) is preferably 300 or more and 20000 or less, more preferably 800 or more and 18000 or less, and further preferably 1000 or more and 16000 or less.
  • A's are each independently an organic group derived from a divalent carboxylic acid, preferably having an alkyl group having 1 to 4 carbon atoms as a substituent.
  • the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, and a tert-butyl group.
  • the position at which the phenylene group or cyclohexylene group is bonded to the adjacent carbonyl carbon may be any of the 1,2-position, 1,3-position, and 1,4-position, but considering the ease of synthesis, the 1,3-position or 1-position , 4th position is preferred.
  • the m R 4 in the formula (2) are each independently a hydrogen atom, 1 to 4 alkyl group having a carbon number (e.g., a methyl group, an ethyl group, a propyl group, an isopropyl group, n- butyl group, sec -Butyl group, isobutyl group, and tert-butyl group), or a group represented by the following formula (3).
  • R ⁇ 5 >, R ⁇ 7 > and m R ⁇ 6 > in Formula (2) show a hydrogen atom or a methyl group each independently.
  • R 5 , R 7 and m R 6 are all hydrogen atoms.
  • a in the formula (3) is the same as in the oligomer represented by the formula (2), and R 8 represents a hydrogen atom or a methyl group.
  • R 8 is a hydrogen atom.
  • M in the formula (2) is an integer of 3 or more and 70 or less, preferably 4 or more and 60 or less, and more preferably 4 or more and 50 or less.
  • the molecular weight of the oligomer represented by the formula (2) is preferably 300 or more and 20000 or less, more preferably 500 or more and 18000 or less, and further preferably 700 or more and 16000 or less.
  • Z's are each independently an organic group derived from a divalent carboxylic acid, and preferably have an alkyl group having 1 to 4 carbon atoms as a substituent.
  • the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, and a tert-butyl group.
  • R 9 in the formula (4) are each independently a linear alkylene group having 1 to 36 carbon atoms (preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms). Or a branched alkylene group is shown. Moreover, R ⁇ 10 > and R ⁇ 11 > in Formula (4) shows a hydrogen atom or a methyl group each independently. Preferably, both R 10 and R 11 are hydrogen atoms.
  • P in Formula (4) is an integer of 1 or more and 10 or less, preferably 1 or more and 9 or less, more preferably 1 or more and 8 or less.
  • Q in Formula (4) is an integer of 5 or more and 50 or less, preferably 5 or more and 45 or less, and more preferably 5 or more and 40 or less.
  • the molecular weight of the oligomer represented by formula (4) is preferably 300 or more and 20000 or less, more preferably 500 or more and 19000 or less, and further preferably 700 or more and 18000 or less.
  • Specific examples other than the (meth) allyl ester resin when the (meth) allyl group-containing compound (A) is an oligomer include polyene compounds derived from substituted or unsubstituted allyl alcohol, polyethylene glycol bis (allyl carbonate) Etc.
  • examples of the (meth) allyl group-containing compound (A) include compounds in which two or more allyl groups are introduced into the polymer skeleton.
  • polymer skeleton examples include a polyethylene skeleton, a polyurethane skeleton, a polyester skeleton, a polyamide skeleton, a polyimide skeleton, a polyoxyalkylene skeleton, and a polyphenylene skeleton. Only one type of (meth) allyl group-containing compound (A) may be used alone, or two or more types may be used in combination.
  • the iodine value of the mixture which mixed all the compounds which belong to the (meth) allyl group containing compound (A) used for the resist ink of this embodiment exists in the range of 20 or more and 240 or less. Preferably they are 30 or more and 210 or less. If the iodine value is in the range of 20 or more and 240 or less, the resist ink can be easily cured in a short time by irradiation with active energy rays or heat.
  • the iodine value described in the present specification is a value obtained by converting the amount of halogen (unit: g) that reacts with 100 g of the target substance into grams of iodine.
  • the thiol compound (B) is not particularly limited as long as it is a compound having two or more mercapto groups in one molecule. Specific examples include a compound having two mercapto groups in one molecule, a compound having three mercapto groups in one molecule, a compound having four mercapto groups in one molecule, and 6 in one molecule. And compounds having one mercapto group.
  • Examples of compounds having two mercapto groups in one molecule are butanediol bis (2-mercaptoacetate), hexanediol bis (2-mercaptoacetate), ethanediol bis (2-mercaptoacetate), butanediol bis.
  • Examples of compounds having three mercapto groups in one molecule include trimethylolpropane tris (2-mercaptoacetate), trimethylolpropane tris (3-mercaptopropionate), trimethylolpropane tris (3- Compounds having three primary mercapto groups in one molecule such as mercapto-2-methylpropionate), trimethylolpropane tris (3-mercaptobutyrate), trimethylolpropane tris (2-mercaptopropio) Nate), trimethylolpropane tris (2-mercaptopropionate), trimethylolpropane tris (4-mercaptovalerate), trimethylolpropane tris (3-mercaptovalerate), 1,3,5-tris (3- Mercaptobutyloxyethyl)- , 3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, etc., a compound having three secondary mercapto groups in one molecule, trimethylolpropan
  • examples of compounds having four mercapto groups in one molecule include four ones in one molecule such as pentaerythritol tetrakis (2-mercaptoacetate) and pentaerythritol tetrakis (3-mercaptopropionate).
  • examples of compounds having 6 mercapto groups in one molecule include six primary mercapto groups in one molecule such as dipentaerythritol hexakis (3-mercapto-2-methylpropionate). Dipentaerythritol hexakis (3-mercaptobutyrate), dipentaerythritol hexakis (2-mercaptopropionate), dipentaerythritol hexakis (2-mercaptoisobutyrate), dipentaerythritol hexa Compounds having six secondary mercapto groups in one molecule such as kiss (4-mercaptovalerate) and dipentaerythritol hexakis (3-mercaptovalerate), dipentaerythritol hexakis (2-mercaptoiso 6 tertiary mercaps of 1 molecule such as butyrate) It can be exemplified compounds having a group.
  • thiol compounds (B) considering the acid resistance and pot life of the resist ink of the present embodiment, it has no primary mercapto group and the number of secondary mercapto groups and tertiary mercapto groups.
  • the total number of the number is preferably 2 or more.
  • a compound having 6 secondary mercapto groups in it, a compound having 6 tertiary mercapto groups in one molecule, and the like are preferable.
  • thiol compound (B) in particular, 1,4-bis (3-mercaptobutyryloxy) butane, pentaerythritol tetrakis (3-mercaptobutyrate), 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione and trimethylolpropane-tris (3-mercaptobutyrate) are more preferred.
  • a thiol compound (B) may be used individually by 1 type, and may use 2 or more types together.
  • the molecular weight of the thiol compound (B) is not particularly limited, but is preferably 200 or more and 1000 or less from the viewpoint of improving the acid resistance of the cured product of the resist ink of this embodiment.
  • the thiol compound (B) can also be easily obtained as a commercial product.
  • commercially available products include 1,4-bis (3-mercaptobutyryloxy) butane (a product manufactured by Showa Denko KK).
  • Karenz MT (trademark) BD1), pentaerythritol tetrakis (3-mercaptobutyrate) (trade name Karenz MT (trademark) PE1 manufactured by Showa Denko KK), 1,3,5-tris (3-mercaptobutyryloxy) Ethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione (trade name Karenz MT (trademark) NR1 manufactured by Showa Denko KK), trimethylolpropane tris (3-mercapto Butyrate) (trade name TPMB manufactured by Showa Denko KK) and the like.
  • the preferred content of the thiol compound (B) in the resist ink of this embodiment is the ratio of the number of (meth) allyl groups in the (meth) allyl group-containing compound (A) to the number of mercapto groups in the thiol compound (B).
  • the contents of the (meth) allyl group-containing compound (A) and the thiol compound (B) in the resist ink may be determined so as to achieve such a ratio.
  • the number of (meth) allyl groups of the (meth) allyl group-containing compound (A) is the total number of (meth) allyl groups of all the compounds belonging to the (meth) allyl group-containing compound (A) (moles).
  • the number of mercapto groups in the thiol compound (B) means the total number (in moles) of mercapto groups in all the compounds belonging to the thiol compound (B).
  • a mercapto group-containing compound other than the thiol compound (B) may be added to the resist ink of the present embodiment.
  • the blending amount of the mercapto group-containing compound other than the thiol compound (B) is 20% by mass of the content of all mercapto group-containing compounds including the thiol compound (B) from the viewpoint of maintaining curability and acid resistance. The following is preferable.
  • the polymerization initiator (C) includes a photopolymerization initiator and a thermal polymerization initiator.
  • the radical polymerization radical is generated by active energy rays and / or heat to polymerize the (meth) allyl group-containing compound (A).
  • Any compound can be used as long as it is a compound that promotes initiation of the polymerization.
  • a polymerization initiator described in Japanese Patent No. 5302688 can be used.
  • a polymerization initiator (C) may be used individually by 1 type, and may be used combining 2 or more types by arbitrary ratios.
  • the photopolymerization initiator and the thermal polymerization initiator may each be used alone, but from the viewpoint of maintaining the printed shape of the resist ink when printing is performed using the resist ink, the polymerization initiator (C) includes It is preferable that a photopolymerization initiator is included.
  • a photoinitiator and a thermal-polymerization initiator can be used together.
  • the type of the photopolymerization initiator is not particularly limited as long as it is a polymerization initiator that is sensitive to the irradiated active energy rays.
  • Active energy rays include near-infrared rays, visible rays, ultraviolet rays, vacuum ultraviolet rays, X-rays, ⁇ rays, electron rays and other electromagnetic waves and particle rays, but as photopolymerization initiators that are sensitive to irradiation with visible rays or ultraviolet rays.
  • Acetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one for example, Darocur 1173 manufactured by BASF
  • benzophenone such as benzophenone, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4-trimethylsilylbenzophenone or the like
  • benzoin such as benzoin, benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl ether, and benzoin isopropyl ether or derivatives thereof.
  • methylphenylglyoxylate, benzoin dimethyl ketal, ethyl (2,4,6-trimethylbenzoyl) phenyl phosphinate (for example, Irgacure TPO manufactured by BASF) is used as a photopolymerization initiator that is sensitive to irradiation with visible light or ultraviolet light.
  • bisacylphosphine oxide compounds such as bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide and bis (2,6-dichlorobenzoyl) -phenylphosphine oxide; Examples thereof include acylphosphine oxide compounds such as 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and 2,4,6-trimethoxybenzoyl-diphenylphosphine oxide.
  • Particularly preferred photopolymerization initiators include diphenyl-2,4,6-trimethylbenzoylphosphine oxide, 2-hydroxy-2-methylpropiophenone, 2-hydroxy-1- (4-isopropenylphenyl) -2-methyl.
  • the product name “ESACURE KTO 46” manufactured by Company A can be preferably used.
  • bis ( ⁇ 5-2,4-cyclopentadien-1-yl) -bis [2,6-difluoro-3- (1H-pyrrole-1-) is used as a photopolymerization initiator that is sensitive to irradiation with visible light or ultraviolet light.
  • a compound generally called a photopolymerization accelerator for example, isoamyl p-dimethylaminobenzoate
  • a hydrogen abstraction type photopolymerization initiator eg, benzophenone series, thioxanthone series
  • Ethyl p-dimethylaminobenzoate is also defined as being included in the photopolymerization initiator in the present invention.
  • acylphosphine oxide compounds include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl -2-Methylamino-1- (4-morpholinophenyl) butanone-1,2,2-dimethoxy-1,2-diphenylethane-1-one and 1-hydroxycyclohexyl phenyl ketone are preferred, 2,4,6- Trimethylbenzoyl-diphenylphosphine oxide, 2,4,6-trimethoxybenzoyl-diphenylphosphine oxide, and 1-hydroxycyclohexyl phenyl ketone are more preferable.
  • the type of thermal polymerization initiator is not particularly limited, and examples thereof include peroxide polymerization initiators such as organic peroxides, azo compounds, persulfates, and redox polymerization initiators. It is done.
  • organic peroxide for example, dialkyl peroxide, acyl peroxide, hydroperoxide, ketone peroxide, peroxy ester, and the like can be used. Specific examples thereof include diisobutyryl peroxide and cumyl peroxyneodecanoate.
  • peroxide-based polymerization initiators include dibenzoyl peroxide, t-butyl permaleate, di-t, t-hexyl peroxide, t-hexyl peroxy-2-ethylhexanoate, and t-butyl hydro gen. A peroxide etc. are mentioned.
  • Examples of the azo compound include 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) and 2,2′-azobis (2,4-dimethylvaleronitrile).
  • Examples of the redox polymerization initiator include a combination of persulfate and sodium bisulfite, a combination of peroxide and sodium ascorbate, and the like.
  • Examples of the persulfate include potassium persulfate and ammonium persulfate.
  • the content of the polymerization initiator (C) in the resist ink of this embodiment is the content of components that do not contribute to the reaction such as the polymerizable initiator (C) and the non-reactive solvent or inorganic filler from the total amount of the resist ink.
  • the content of the polymerization initiator (C) is preferably 0.01 parts by weight or more and 10 parts by weight or less when the amount obtained by subtracting 100 parts by weight is 100 parts by weight. More preferably, it is 0.3 to 7 parts by mass, and particularly preferably 0.4 to 3 parts by mass. If content of a polymerization initiator (C) is in said numerical range, while being able to obtain sufficient hardening rate, the mechanical strength of hardened
  • the resist ink of this embodiment is composed of a (meth) allyl group-containing compound (A), a thiol compound (B), and a polymerization initiator (C)
  • the (meth) allyl group-containing compound (A) and the total content of the thiol compound (B) are 100 parts by mass
  • the content of the polymerization initiator (C) is preferably 0.01 parts by mass or more and 10 parts by mass or less.
  • the resist ink of the present embodiment comprises a (meth) allyl group-containing compound (A), a thiol compound (B), a polymerization initiator (C), and a (meth) acryloyl group-containing compound (D) described later.
  • the content of is preferably 0.01 parts by mass or more and 10 parts by mass or less.
  • the resist ink of this embodiment may further contain a (meth) acryloyl group-containing compound (D).
  • the (meth) acryloyl group-containing compound (D) is not particularly limited as long as it is a compound containing a (meth) acryloyl group, but examples thereof include epoxy (meth) acrylate, (poly) ester (meta) ) Acrylate, (poly) carbonate (meth) acrylate, hydrogenated polybutadiene (meth) acrylate, (poly) ether (meth) acrylate, (poly) urethane (meth) acrylate, and the like.
  • epoxy (meth) acrylate, (poly) ester (meth) acrylate, (poly) carbonate (meth) acrylate, and hydrogenated polybutadiene (meth) acrylate are preferable, and epoxy (meth) acrylate, (poly ) Carbonate (meth) acrylate, more preferably epoxy (meth) acrylate.
  • the (meth) acryloyl group-containing compound (D) is preferably a compound having at least one structure selected from an alicyclic structure and an aromatic ring structure in the molecule. Furthermore, the (meth) acryloyl group-containing compound (D) is preferably a compound having two or more (meth) acryloyl groups from the viewpoint of curability of the resist ink.
  • Epoxy (meth) acrylate means all compounds obtained by reacting an epoxy resin having an epoxy group with a monocarboxylic acid having a (meth) acryloyl group.
  • the epoxy resin is preferably a compound having two or more epoxy groups in one molecule, specifically, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin.
  • Bisphenol type epoxy resins such as hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol F type epoxy resin, hydrogenated bisphenol S type epoxy resin, hydrogenated bisphenol AD type epoxy resin, and tetrabromobisphenol A type epoxy resin.
  • ortho-cresol novolac epoxy resin examples include ortho-cresol novolac epoxy resin, phenol novolac epoxy resin, naphthol novolac epoxy resin, bisphenol A novolac epoxy resin, brominated phenol novolac epoxy resin, alkylphenol novolac epoxy resin, bisphenol S novolac epoxy resin, methoxy
  • novolak type epoxy resins such as group-containing novolak type epoxy resins and brominated phenol novolac type epoxy resins.
  • phenol aralkyl type epoxy resin commonly known as epoxidized xyloc resin
  • resorcin diglycidyl ether hydroquinone diglycidyl ether
  • catechol diglycidyl ether catechol diglycidyl ether
  • biphenyl type epoxy resin tetramethylbiphenyl type epoxy resin, etc.
  • Type epoxy resin triglycidyl isocyanurate, triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, biphenyl modified novolak type epoxy resin (phenolic nucleus linked by bismethylene group) Epoxidized polyhydric phenol resins), methoxy group-containing phenol aralkyl resins, and the like.
  • Epoxy (meth) acrylate can also be easily obtained as a commercial product.
  • examples of commercially available epoxy (meth) acrylates include VR-77 manufactured by Showa Denko KK, Epoxy ester 40EM, Epoxy ester 30002M, Epoxy ester 3002A, Epoxy ester 3000MK, and Epoxy ester 3000A manufactured by Kyoeisha Chemical Co., Ltd. , EBECRYL600, EBECRYL648, EBECRYL3700, etc. manufactured by Daicel Ornex Co., Ltd. can be mentioned.
  • (poly) ester (meth) acrylate means a compound having at least one ester bond other than a (meth) acryloyloxy group and having at least one (meth) acrylate group.
  • (Poly) ester (meth) acrylate can also be easily obtained as a commercial item. Examples of commercially available (poly) ester (meth) acrylates include EBECRYL450, EBECRYL810, EBECRYL811, EBECRYL812, EBECRYL1830, EBECRYL846, EBECRYL851 and EBECRYL8551, EBECRYL851 and EBECRYL851. .
  • (poly) carbonate (meth) acrylate means a compound having one or more carbonate groups and one or more (meth) acrylate groups.
  • Synthesis methods of (poly) carbonate (meth) acrylate include dehydrochlorination reaction of (meth) acrylic acid chloride and polycarbonate polyol, direct dehydration reaction of (meth) acrylic acid and (poly) carbonate polyol, (meth) A transesterification reaction between a lower alkyl ester of acrylic acid and a (poly) carbonate polyol is used.
  • (Poly) carbonate (meth) acrylate can also be easily obtained as a commercial product.
  • Examples of the commercially available (poly) carbonate (meth) acrylate include a compound represented by the following formula (5), which is a polycarbonate diol diacrylate manufactured by Ube Industries, Ltd.
  • formula (5) is a polycarbonate diol diacrylate manufactured by Ube Industries, Ltd.
  • k is an integer of 1 or more.
  • hydrogenated polybutadiene (meth) acrylate means a compound having a hydrogenated polybutadiene structure and a (meth) acrylate structure in the molecule.
  • esterification reaction of hydrogenated polybutadiene polyol and (meth) acrylic acid As a synthesis method of hydrogenated polybutadiene (meth) acrylate, esterification reaction of hydrogenated polybutadiene polyol and (meth) acrylic acid, transesterification reaction of hydrogenated polybutadiene polyol and (meth) acrylic acid ester, hydrogenated polybutadiene polyol and
  • An addition reaction of isocyanato group-containing (meth) acrylate, an addition reaction of hydrogenated polybutadiene polyol, polyisocyanate, and alcoholic hydroxyl group-containing (meth) acrylate is preferably used.
  • Hydrogenated polybutadiene (meth) acrylate can also be easily obtained as a commercial product.
  • the commercially available hydrogenated polybutadiene (meth) acrylate include NISSO-PB TEAI-1000 manufactured by Nippon Soda Co., Ltd., which is an adduct of hydrogenated polybutadiene polyol, polyisocyanate, and alcoholic hydroxyl group-containing acrylate, hydrogenated polybutadiene.
  • Examples thereof include SPBDA-S30 manufactured by Osaka Organic Chemical Industry Co., Ltd., which is a diacrylate.
  • (poly) ether (meth) acrylate means a compound having at least one ether bond and having at least one (meth) acrylate group in the molecule, such as polyethylene glycol diacrylate, polypropylene. Examples include glycol diacrylate and polytetramethylene glycol diacrylate.
  • (poly) urethane (meth) acrylate means a compound having one or more urethane bonds in the molecule and having one or more (meth) acrylate groups.
  • polyol, polyisocyanate and hydroxyl A compound obtained by performing a polyaddition reaction using a group-containing (meth) acrylate as an essential raw material, or a compound obtained by performing a polyaddition reaction using a polyol and an isocyanate group-containing (meth) acrylate as an essential raw material can be mentioned.
  • the number average molecular weight of the (meth) acryloyl group-containing compound (D) is not limited, but is preferably 400 or more and more preferably 600 or more from the viewpoint of acid resistance.
  • the content is preferably as follows from the viewpoint of acid resistance. That is, when the total content of the (meth) allyl group-containing compound (A), the thiol compound (B), and the (meth) acryloyl group-containing compound (D) is 100 parts by mass, the (meth) acryloyl group
  • the content of the containing compound (D) is preferably 10 parts by mass or more and 80 parts by mass or less, more preferably 20 parts by mass or more and 70 parts by mass or less, and 40 parts by mass or more and 70 parts by mass or less. Further preferred.
  • the content of the acryloyl group-containing compound (D) is within the above range, the effect of improving the mechanical properties of the cured product by the blending of the (meth) acryloyl group-containing compound (D) is sufficiently expressed, and the resist ink Volume shrinkage during curing is difficult to increase.
  • the resist ink of the present embodiment may contain a polymerization inhibitor as necessary in order to suppress radical polymerization during storage and improve storage stability.
  • the type of the polymerization inhibitor is not particularly limited.
  • methylhydroquinone, pyrogallol, and tertiary butylhydroquinone are particularly preferred from the viewpoint of the storage stability of the resist ink.
  • These polymerization inhibitors may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the content of the polymerization inhibitor in the resist ink of the present embodiment is not particularly limited, but from the viewpoint of storage stability of the resist ink, the (meth) allyl group-containing compound (A), the thiol compound (B), The total content of 100 parts by mass (when the resist ink of this embodiment contains the (meth) acryloyl group-containing compound (D), the (meth) allyl group-containing compound (A), the thiol compound (B), When the total content of the (meth) acryloyl group-containing compound (D) is 100 parts by mass), the content of the polymerization inhibitor is preferably less than 0.1 parts by mass, and 0.0001 parts by mass or more The amount is more preferably 0.05 parts by mass or less.
  • the resist ink of the present embodiment may contain an antioxidant as necessary in order to suppress coloring of the cured product of the resist ink at a high temperature.
  • the type of the antioxidant is not particularly limited.
  • pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate]
  • octadecyl-3- (3,5 -Di-tert-butyl-4-hydroxyphenyl) propionate
  • hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate]
  • thiodiethylenebis [3- (3,5- Di-tert-butyl-4-hydroxyphenyl) propionate]
  • 4,6-bis (octylthiomethyl) -o-cresol 2,4-bis [(dodecylthio) methyl] -6-methylphenol
  • 1,3, 5-Tris (3,5-
  • antioxidants tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) -s-triazine- is used from the viewpoint of suppressing coloring of a cured resist ink at high temperature.
  • 2,4,6- (1H, 3H, 5H) -trione, octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) prothionate are preferred.
  • the content of the antioxidant in the resist ink of the present embodiment is not particularly limited. From the viewpoint of suppressing coloring of the cured product of the resist ink at a high temperature, the (meth) allyl group-containing compound (A) And 100 parts by mass of the total content of the thiol compound (B) (when the resist ink of this embodiment contains the (meth) acryloyl group-containing compound (D), the (meth) allyl group-containing compound (A)
  • the total content of the thiol compound (B) and the (meth) acryloyl group-containing compound (D) is preferably 100 parts by mass), and the content of the antioxidant is preferably less than 0.1 parts by mass. More preferably, it is 0.0001 parts by mass or more and 0.05 parts by mass or less.
  • the resist ink of this embodiment contains the (meth) allyl group-containing compound (A), the thiol compound (B), and the polymerization initiator (C).
  • the (meth) acryloyl group-containing compound (D), a polymerization inhibitor, and an antioxidant which are optional components, may be contained, and other components as long as the purpose of the present invention is not impaired. May be contained.
  • the resist ink of this embodiment does not need to contain a solvent as another component, and may contain a solvent, but it is preferable not to contain a solvent.
  • the resist ink of this embodiment may contain a thixotropic agent, a tackifier, etc. as other components.
  • the type of thixotropic agent is not particularly limited, and any thixotropic agent such as an inorganic thixotropic agent or an organic thixotropic agent can be used.
  • inorganic thixotropic agent examples include fumed silica (SiO 2 ) represented by Aerosil (trademark), alumina (Al 2 O 3 ), titania (TiO 2 ), tantalum oxide (Ta 2 O 5 ), zirconia ( ZrO 2 ), silicon nitride (Si 3 N 4 ), barium titanate (BaO ⁇ TiO 2 ), barium carbonate (BaCO 3 ), lead titanate (PbO ⁇ TiO 2 ), lead zirconate titanate (PZT), titanium zirconate titanate, lead lanthanum (PLZT), gallium oxide (Ga 2 O 3), spinel (MgO ⁇ Al 2 O 3) , mullite (3Al 2 O 3 ⁇ 2SiO 2 ), cordierite (2MgO ⁇ 2Al 2 O 3 ⁇ 5SiO 2), talc (3MgO ⁇ 4SiO 2 ⁇ H 2 O), aluminum titanate (TiO
  • Hydrotalcite is a kind of a naturally occurring clay mineral represented by Mg 6 Al 2 (OH) 16 CO 3 .4H 2 O and the like, and is a layered inorganic compound. Further, hydrotalcite, for example, can be obtained by combining the Mg1-xAlx (OH) 2 ( CO 3) x / 2 ⁇ mH 2 O , and the like. That is, hydrotalcite is an Mg / Al-based layered compound, and anions such as chloride ions (Cl ⁇ ) and / or sulfate ions (SO 4 2 ⁇ ) are fixed by ion exchange with carbonate groups between layers.
  • anions such as chloride ions (Cl ⁇ ) and / or sulfate ions (SO 4 2 ⁇ ) are fixed by ion exchange with carbonate groups between layers.
  • chloride ions (Cl ⁇ ) and sulfate ions (SO 4 2 ⁇ ) that cause migration of copper and tin can be captured, and the insulation reliability can be improved.
  • examples of commercially available hydrotalcite include STABIACE HT-1, STABIACE HT-7 and STABIACE HT-P from Sakai Chemical Co., Ltd., DHT-4A, DHT-4A2, and DHT-4C from Kyowa Chemical Industry Co., Ltd. Is mentioned.
  • organic thixotropic agent fine particles of a heat-resistant resin having an amide bond, an imide bond, an ester bond or an ether bond are preferable.
  • examples include fatty acid amide thixotropic agents and ethyl cellulose thixotropic agents.
  • the fatty acid amide thixotropic agent and the ethyl cellulose type thixotropic agent can also be easily obtained as commercial products.
  • Examples of commercially available fatty acid amide thixotropic agents include Disparon (trademark) 6500, Disparon (trademark) 6650, Disparon (trademark) 6700 and the like manufactured by Enomoto Kasei Co., Ltd.
  • Examples of commercially available ethylcellulose thixotropic agents include ETHOCEL TM 45, ETHOCEL TM 100, and ETHOCEL TM 200 manufactured by Dow Chemical Company.
  • the tackifier is a substance that is added to a polymer compound typified by an elastomer having rubber elasticity to give an adhesive function.
  • Tackifiers are much smaller in molecular weight than high molecular compounds typified by elastomers, and are generally compounds in the oligomer range with molecular weights of several hundred to several thousand. They are glassy at room temperature, and themselves are rubber elastic. It has the property of not showing.
  • a petroleum resin tackifier As the tackifier, a petroleum resin tackifier, a terpene resin tackifier, a rosin resin tackifier, a coumarone indene resin tackifier, a styrene resin tackifier, or the like can be generally used.
  • Examples of petroleum resin tackifiers include aliphatic petroleum resins, aromatic petroleum resins, aliphatic-aromatic copolymer petroleum resins, alicyclic petroleum resins, dicyclopentadiene resins, and hydrogenated products thereof. Of the modified product.
  • the synthetic petroleum resin may be C5 or C9.
  • terpene resin tackifier examples include ⁇ -pinene resin, ⁇ -pinene resin, terpene-phenol resin, aromatic modified terpene resin, hydrogenated terpene resin and the like. Many of these terpene resins are resins having no polar group.
  • rosin resin tackifiers include rosins such as gum rosin, tall oil rosin and wood rosin, modified rosins such as hydrogenated rosin, disproportionated rosin, polymerized rosin and maleated rosin, rosin glycerin ester and hydrogenated rosin ester. And rosin esters such as hydrogenated rosin glycerin ester. These rosin resins have polar groups. These tackifiers may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the resist ink of this embodiment may contain an antifoaming agent as another component.
  • the type of antifoaming agent is not particularly limited, and specific examples include BYK-077 manufactured by Big Chemie Japan, SN deformer 470 manufactured by San Nopco, TSA750S manufactured by GE Toshiba Silicone, Toray Silicone antifoaming agents such as silicone oil SH-203 manufactured by Dow Corning Co., Ltd., acrylic polymer antifoaming agents such as Dappo SN-348, Dappo SN-354, and Dappo SN-368 manufactured by San Nopco Co., Ltd.
  • Examples include acetylenic diol defoamers such as Surfynol DF-110D and Surfynol DF-37 manufactured by Shin Chemical Co., Ltd., and fluorine-containing silicone defoamers such as FA-630 manufactured by Shin-Etsu Chemical Co., Ltd. be able to.
  • the resist ink of the present embodiment comprises a (meth) acryloyl group as necessary together with a (meth) allyl group-containing compound (A), a thiol compound (B), and a polymerization initiator (C).
  • the compound (D), the polymerization inhibitor, the antioxidant, and other components can be appropriately mixed and prepared.
  • the content of the polymerization initiator (C) is 0.01 parts by mass or more and 10 parts by mass. It is good to mix so that it may become in the range below a mass part.
  • the method for preparing the resist ink of the present embodiment is not particularly limited, and the (meth) allyl group-containing compound (A), the thiol compound (B), the polymerization initiator (C), the (meth) acryloyl group-containing compound ( Any method may be used as long as it can mix and disperse each raw material of resist ink including D). Examples of the method of mixing and dispersing include the following methods.
  • Each raw material is put into a container such as a glass beaker, a can, a plastic cup, or an aluminum cup and kneaded with a stirring rod, a spatula, or the like.
  • B Each raw material is kneaded with a double helical ribbon blade, a gate blade, or the like.
  • Each raw material is kneaded with a planetary mixer.
  • D Each raw material is kneaded by a bead mill.
  • Each raw material is kneaded with three rolls.
  • Each raw material is kneaded by an extruder-type kneading extruder.
  • G Each raw material is kneaded by a rotating / revolving mixer.
  • each raw material can be performed in an arbitrary order, and all the raw materials may be added simultaneously or sequentially.
  • active energy ray illumination is performed through a filter that removes light having an absorption wavelength at which the photopolymerization initiator decomposes during the pre-curing treatment such as handling and mixing of the above raw materials. It can be carried out under conditions where the polymerization initiator (C) does not act before the curing treatment, such as under or without irradiation with active energy rays, or under a temperature at which the thermal polymerization initiator acts.
  • cured material of resist ink of this embodiment as a protective film of fine patterns, such as wiring, a screen printing method is used preferably for printing of resist ink.
  • the resist ink is cured by irradiating the resist ink of the present embodiment with active energy rays or heating, and a cured product is obtained.
  • Active energy rays used at the time of curing include near-infrared rays, visible rays, ultraviolet rays, vacuum ultraviolet rays, X-rays, ⁇ -rays, electromagnetic waves such as electron rays, and particle rays, but since inexpensive devices can be used, ultraviolet rays and Visible light is preferred.
  • Various light sources can be used as the light source for curing the resist ink of the present embodiment with ultraviolet rays or visible rays. Examples thereof include a black light, a UV-LED lamp, a high-pressure mercury lamp, a pressurized mercury lamp, a metal halide lamp, a xenon lamp, an electrodeless discharge lamp, and a halogen lamp.
  • black light is a near-ultraviolet light having a wavelength of 300 nm or more and 430 nm or less (peak 350 nm) only when a near-ultraviolet phosphor is applied to a special outer glass cut from visible light and ultraviolet light having a wavelength of 300 nm or less. It is a lamp that radiates.
  • the UV-LED lamp is a lamp using a light emitting diode that emits ultraviolet rays.
  • a high-pressure mercury lamp and a metal halide lamp are preferable from the viewpoint of curability.
  • an LED lamp UV-LED lamp
  • the irradiation amount of the active energy ray may be an amount sufficient to cure the resist ink of this embodiment, and the composition, usage amount, thickness, shape of the cured product to be formed, etc. of the resist ink of this embodiment. Can be selected accordingly.
  • ultraviolet rays are radiated onto the coating film formed by coating the resist ink of the present embodiment is preferably 100 mJ / cm 2 or more 5000 mJ / cm 2 or less of the exposure amount, and more preferably 300 mJ / cm 2 or more An exposure amount of 3000 mJ / cm 2 or less can be employed.
  • the measurement wavelength of said exposure amount is 365 nm.
  • the application (coating) method in the case where the resist ink of the present embodiment is applied onto a substrate to form a coating film is not particularly limited.
  • natural coater, curtain flow coater, comma coater, gravure coater, micro gravure coater, die coater, curtain coater, kiss roll, squeeze roll, reverse roll, air blade, knife belt coater, floating knife A method using a knife over roll, a knife on blanket or the like.
  • the method using an inkjet printer, a screen printer, etc. can also be mentioned.
  • the polymerization initiator (C) includes a photopolymerization initiator as described above. Is preferred.
  • the manufacturing method of the protective film of wiring of this embodiment is provided with the following coating processes and hardening processes.
  • the covering step is a step in which a resist ink is provided in a film shape by a printing method, for example, on a substrate having wiring (for example, a printed wiring board), and the wiring is covered with a resist ink film.
  • the resist ink film may be disposed on the entire surface of the substrate, or may be disposed on a part of the surface as long as the wiring can be covered.
  • the printing method is not particularly limited, and examples thereof include a screen printing method, a roll coater method, a spray method, and a curtain coater method.
  • the screen printing method is preferable from the viewpoint of controlling the shape pattern of the resist ink film as a printed matter.
  • the curing step a part or all of the region including the region covering the wiring in the resist ink film is irradiated with active energy rays having a wavelength that generates a polymerizable radical species in the polymerization initiator (C).
  • the resist ink in the region irradiated with the active energy ray is cured to form a protective film for the wiring.
  • Examples of active energy rays used in the curing step include near infrared rays, visible rays, ultraviolet rays, vacuum ultraviolet rays, X-rays, ⁇ rays, electron rays and other electromagnetic waves and particle rays, but ultraviolet rays and visible rays are preferable, and ultraviolet rays are preferred. Is more preferable.
  • the light source of ultraviolet light and visible light is not particularly limited, and for example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, a metal halide lamp, a halogen lamp, or the like can be used.
  • the dose of visible light varies depending on the composition or the like of the resist ink may be a 100 mJ / cm 2 or more 5000 mJ / cm 2 within the following ranges.
  • the measurement wavelength of said exposure amount is 365 nm.
  • a curing step by heating can be performed after the curing step by irradiation with active energy rays.
  • the heating temperature (thermosetting temperature) in the curing step by heating varies depending on the cleavage temperature of the thermal polymerization initiator, but is preferably 80 ° C. or higher and 170 ° C. or lower.
  • the heating time (thermal curing time) in the curing step by heating is the same, but is preferably 5 minutes or longer and 3 hours or shorter, more preferably 10 minutes or longer and 2 hours or shorter.
  • the thickness of the protective film of this embodiment may be appropriately set according to the use of the protective film, but is preferably 0.1 ⁇ m or more and 30 ⁇ m or less, more preferably 1 ⁇ m or more and 20 ⁇ m or less, and further preferably 2 ⁇ m or more and 15 ⁇ m or less.
  • the protective film of this embodiment may contain other components other than the hardened
  • this embodiment shows an example of this invention and this invention is not limited to this embodiment.
  • various changes or improvements can be added to the present embodiment, and forms to which such changes or improvements are added can also be included in the present invention.
  • Examples 1 to 11 and Comparative Examples were prepared by mixing various raw materials of (meth) allyl group-containing compound (A), thiol compound (B), polymerization initiator (C), and (meth) acryloyl group-containing compound (D).
  • A allyl group-containing compound
  • B thiol compound
  • C polymerization initiator
  • D acryloyl group-containing compound
  • resist inks were prepared. Various raw materials used for preparing the resist ink will be described below.
  • (Ii) Thiol compound (B) The following three compounds (ii-1) to (ii-3) were used as the thiol compound (B).
  • (Ii-1) Pentaerythritol-tetrakis (3-mercaptobutyrate) (trade name Karenz MT (trademark) PE1, manufactured by Showa Denko KK, molecular weight 545, number of mercapto groups 4)
  • (Ii-3) Pentaerythritol-tetrakis (3-mercaptopropionate) (trade name PEMP, molecular weight 489, number 4 of mercap
  • (Iii) Polymerization initiator (C) The following three compounds (iii-1) to (iii-3) were used as the polymerization initiator (C).
  • (Iii-1) 2,4,6-trimethylbenzoylphosphine oxide (a mixture of ESACURE KTO46, a polymer having an ⁇ -hydroxyketone group and a benzophenone derivative manufactured by DKSH Japan)
  • the following production examples 1 to 5 show production methods of the above-mentioned allyl ester resins A to D and urethane acrylate A.
  • diallyl terephthalate is removed from the allyl ester resin A by further heating for 1 hour and holding at a temperature of 190 ° C. and a pressure of 0.13 kPa for an additional hour, so that 445 g Allyl ester resin A was obtained.
  • the iodine value of allyl ester resin A measured by a method based on JIS K 0070 was 77.
  • Allyl ester resin A was analyzed using a gas chromatography GC-14B (detector: hydrogen flame ionization detector, column: OV-17 (0.5 m), temperature condition: 160 ° C. constant) manufactured by Shimadzu Corporation.
  • the allyl ester resin A contained 1% by mass of diallyl terephthalate, and the remaining 99% by mass was a transesterification product (allyl ester oligomer) of diallyl terephthalate and propylene glycol.
  • the reaction was continued at 80 ° C. for 3 hours. Thereafter, the infrared absorption spectrum of the reaction product was measured. When it was confirmed in the infrared absorption spectrum that the absorption of the isocyanato group had disappeared, the reaction was terminated and urethane acrylate A was obtained.
  • the molecular weight of the oligomer or polymer in each Example and a comparative example is the number average molecular weight of polystyrene conversion measured by GPC method.
  • the measurement conditions for GPC are as follows.
  • Resist ink is prepared by mixing the (meth) allyl group-containing compound (A), the thiol compound (B), the polymerization initiator (C), and the (meth) acryloyl group-containing compound (D) at a mass ratio shown in Table 1.
  • Table 1 “(A) / (B) functional group number ratio” is the ratio of the number of (meth) allyl groups in the (meth) allyl group-containing compound (A) to the number of mercapto groups in the thiol compound (B). (Number of (meth) allyl groups / number of mercapto groups).
  • mass ratio of (D) is the total content of the (meth) allyl group-containing compound (A), the thiol compound (B), and the (meth) acryloyl group-containing compound (D). When it is 100 parts by mass, the content of the (meth) acryloyl group-containing compound (D) is shown.
  • the resist ink film was cured by irradiating UV light with an exposure amount of 2 J / cm 2 using a conveyor type UV irradiator ECS-4011GX (high pressure mercury lamp) manufactured by IGraphics Co., Ltd.
  • a test body having a protective film made of a cured product was obtained.
  • the measurement wavelength of said exposure amount is 365 nm.
  • the obtained specimen was washed with an aqueous sulfuric acid solution having a concentration of 5% by mass, and then immersed in an electroless tin plating solution 580M12Z manufactured by Ishihara Chemical Co., Ltd. at 60 ° C. for 4 minutes. At this time, half of the protective film made of a resist ink cured product was not immersed in the electroless tin plating solution so that a portion not subjected to the plating treatment could be observed.
  • the test specimen was taken out from the electroless tin plating solution, washed with warm water repeatedly, and then subjected to a eutectic treatment at 120 ° C. for 90 minutes with a blow type constant temperature dryer. And about this test body, the following 3 points
  • the resist ink was a (meth) allyl group-containing compound (A), a thiol compound (B), and a polymerization initiator (C). Therefore, even when immersed in a strongly acidic electroless tin plating solution, peeling of the protective film, penetration of the plating, and coloring of the protective film hardly occurred.
  • the cured resist inks of Comparative Examples 1 to 4 have acid resistance because the resist ink does not contain at least one of the (meth) allyl group-containing compound (A) and the thiol compound (B). It was insufficient. For this reason, when immersed in a strongly acidic electroless tin plating solution, the protective film peeled off, and evaluation of the penetration of the plating and coloring of the protective film could not be performed.

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  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Materials For Photolithography (AREA)
  • Non-Metallic Protective Coatings For Printed Circuits (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)

Abstract

L'invention concerne une encre de réserve qui est capable de former un produit durci qui présente une excellente résistance aux acides. L'encre de réserve selon l'invention contient un composé (A) contenant un groupe (méth)allyle ayant au moins deux groupes (méth)allyle dans une molécule, un composé (B) thiol ayant deux groupes mercapto ou plus dans une molécule, et un initiateur de polymérisation (C).
PCT/JP2017/011481 2016-03-31 2017-03-22 Encre de réserve, produit durci de celle-ci, film protecteur pour lignes de câblage et procédé de production d'un film protecteur pour lignes de câblage Ceased WO2017170050A1 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017206572A (ja) * 2016-05-16 2017-11-24 株式会社大阪ソーダ 光硬化性組成物、及びその硬化物
JP2020158650A (ja) * 2019-03-27 2020-10-01 太陽インキ製造株式会社 硬化性組成物、およびその硬化物
CN114127202A (zh) * 2019-07-18 2022-03-01 日产化学株式会社 包含具有固化性官能团的化合物的高低差基板被覆用组合物
CN114874658A (zh) * 2021-12-03 2022-08-09 佛山市西伦化工有限公司 一种抗蚀刻的uv油墨及其制备方法
JP2024041410A (ja) * 2022-09-14 2024-03-27 サカタインクス株式会社 活性エネルギー線硬化型組成物
JP2024071426A (ja) * 2019-12-23 2024-05-24 株式会社リコー 活性エネルギー線硬化型組成物、活性エネルギー線硬化型インク組成物、活性エネルギー線硬化型インクジェット用インク組成物、組成物収容容器、２次元又は３次元の像形成装置、２次元又は３次元の像形成方法、硬化物、及び加飾体
JP7669569B1 (ja) 2024-06-07 2025-04-28 サカタインクス株式会社 印刷物の製造方法
CN120574500A (zh) * 2025-08-04 2025-09-02 金阳(泉州)新能源科技有限公司 用于背接触电池的高透光绝缘油墨及其制备方法

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TWI767248B (zh) 2020-06-10 2022-06-11 新應材股份有限公司 白色感光性樹脂組成物、白色隔壁、光轉換層以及光發射裝置
JP2023121316A (ja) * 2022-02-21 2023-08-31 サカタインクス株式会社 活性エネルギー線硬化型インキ組成物

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010132751A (ja) * 2008-12-03 2010-06-17 Showa Denko Kk 多価アリルエステル化合物の脱色方法
JP2010285519A (ja) * 2009-06-10 2010-12-24 Kaneka Corp 光硬化性組成物およびそれを用いた絶縁性薄膜および薄膜トランジスタ
JP2013194189A (ja) * 2012-03-22 2013-09-30 Nippon Shokubai Co Ltd 硬化性樹脂組成物および感光性樹脂組成物
WO2014203779A1 (fr) * 2013-06-17 2014-12-24 昭和電工株式会社 Composition durcissable de type ène-thiol et produit durci de celle-ci

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2009011211A1 (ja) * 2007-07-13 2010-09-16 昭和電工株式会社 硬化性組成物およびその硬化物

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010132751A (ja) * 2008-12-03 2010-06-17 Showa Denko Kk 多価アリルエステル化合物の脱色方法
JP2010285519A (ja) * 2009-06-10 2010-12-24 Kaneka Corp 光硬化性組成物およびそれを用いた絶縁性薄膜および薄膜トランジスタ
JP2013194189A (ja) * 2012-03-22 2013-09-30 Nippon Shokubai Co Ltd 硬化性樹脂組成物および感光性樹脂組成物
WO2014203779A1 (fr) * 2013-06-17 2014-12-24 昭和電工株式会社 Composition durcissable de type ène-thiol et produit durci de celle-ci

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* Cited by examiner, † Cited by third party
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JP2017206572A (ja) * 2016-05-16 2017-11-24 株式会社大阪ソーダ 光硬化性組成物、及びその硬化物
JP2020158650A (ja) * 2019-03-27 2020-10-01 太陽インキ製造株式会社 硬化性組成物、およびその硬化物
JP7551278B2 (ja) 2019-03-27 2024-09-17 太陽ホールディングス株式会社 硬化性組成物、およびその硬化物
CN114127202A (zh) * 2019-07-18 2022-03-01 日产化学株式会社 包含具有固化性官能团的化合物的高低差基板被覆用组合物
CN114127202B (zh) * 2019-07-18 2023-09-05 日产化学株式会社 包含具有固化性官能团的化合物的高低差基板被覆用组合物
JP2024071426A (ja) * 2019-12-23 2024-05-24 株式会社リコー 活性エネルギー線硬化型組成物、活性エネルギー線硬化型インク組成物、活性エネルギー線硬化型インクジェット用インク組成物、組成物収容容器、２次元又は３次元の像形成装置、２次元又は３次元の像形成方法、硬化物、及び加飾体
CN114874658A (zh) * 2021-12-03 2022-08-09 佛山市西伦化工有限公司 一种抗蚀刻的uv油墨及其制备方法
JP2024041410A (ja) * 2022-09-14 2024-03-27 サカタインクス株式会社 活性エネルギー線硬化型組成物
JP7846592B2 (ja) 2022-09-14 2026-04-15 サカタインクス株式会社 活性エネルギー線硬化型組成物
JP7669569B1 (ja) 2024-06-07 2025-04-28 サカタインクス株式会社 印刷物の製造方法
JP2025184540A (ja) * 2024-06-07 2025-12-18 サカタインクス株式会社 印刷物の製造方法
CN120574500A (zh) * 2025-08-04 2025-09-02 金阳(泉州)新能源科技有限公司 用于背接触电池的高透光绝缘油墨及其制备方法
CN120574500B (zh) * 2025-08-04 2025-10-31 金阳(泉州)新能源科技有限公司 用于背接触电池的高透光绝缘油墨及其制备方法

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