WO2018123826A1 - Composition de résine photodurcissable négative, film sec, produit durci et carte de câblage imprimée - Google Patents

Composition de résine photodurcissable négative, film sec, produit durci et carte de câblage imprimée Download PDF

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Publication number
WO2018123826A1
WO2018123826A1 PCT/JP2017/046022 JP2017046022W WO2018123826A1 WO 2018123826 A1 WO2018123826 A1 WO 2018123826A1 JP 2017046022 W JP2017046022 W JP 2017046022W WO 2018123826 A1 WO2018123826 A1 WO 2018123826A1
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Prior art keywords
compound
resin
resin composition
group
photocurable resin
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PCT/JP2017/046022
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English (en)
Japanese (ja)
Inventor
歩 嶋宮
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太陽インキ製造株式会社
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Priority claimed from JP2017058961A external-priority patent/JP6877202B2/ja
Application filed by 太陽インキ製造株式会社 filed Critical 太陽インキ製造株式会社
Publication of WO2018123826A1 publication Critical patent/WO2018123826A1/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
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/075—Silicon-containing compounds
    • 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 negative photocurable resin composition, a dry film, a cured product, and a printed wiring board.
  • a positive or negative photosensitive composition is used for forming a resin layer such as an interlayer insulating layer or a solder resist layer (for example, Patent Document 1).
  • the photoacid generator contained as one of its components is very expensive, which causes a problem in cost.
  • diazonaphthoquinone which is a typical photoacid generator, has a problem when a thick film (mainly 10 ⁇ m or more) is formed (for example, Patent Document 2) because foaming can occur by denitrification reaction.
  • a negative photosensitive composition excellent in resolution ie, a negative photocurable resin composition
  • the resin layer of the printed wiring board as described above is required to have high heat resistance and high elongation from the viewpoint of reliability and the like, but the heat resistance and elongation are a trade-off. There was a relationship, and the balance was not enough.
  • an object of the present invention is to provide a negative photocurable resin composition that is excellent in resolution and can form a cured product having high heat resistance and high elongation, a dry film having a resin layer obtained from the composition, It is providing the hardened
  • the negative photocurable resin composition of the present invention comprises (A) an alkali-soluble resin, (B) an organosiloxane compound having a cyclic siloxane skeleton having 6 or more members, and (C) a photopolymerization initiator.
  • the (B) organosiloxane compound having a 6-membered or higher cyclic siloxane skeleton has a skeleton represented by the following general formula. (In the formula, n represents an integer of 1 or more)
  • the (B) organosiloxane compound having a 6-membered or higher cyclic siloxane skeleton preferably has a thermosetting reactive group.
  • thermosetting reactive group is preferably an epoxy group.
  • the (B) organosiloxane compound having a 6-membered or higher cyclic siloxane skeleton preferably has a photosensitive group.
  • the photosensitive group is preferably an ethylenically unsaturated group.
  • the negative photocurable resin composition of the present invention preferably further contains a compound having an ethylenically unsaturated group.
  • the compound having an ethylenically unsaturated group is preferably a bifunctional or higher functional (meth) acrylate compound.
  • the compound having an ethylenically unsaturated group is preferably an acrylate compound having a (meth) acryl equivalent of 100 or more.
  • the dry film of the present invention is characterized by having a resin layer obtained by applying and drying the negative photocurable resin composition on the film.
  • the cured product of the present invention is obtained by curing the negative photocurable resin composition or the resin layer of the dry film.
  • the printed wiring board of the present invention is characterized by having the cured product.
  • a negative photocurable resin composition that is excellent in resolution and capable of forming a cured product having high heat resistance and high elongation, a dry film having a resin layer obtained from the composition, and curing thereof And a printed wiring board having the cured product.
  • the negative photocurable resin composition of the present invention comprises (A) an alkali-soluble resin, (B) an organosiloxane compound having a cyclic siloxane skeleton having 6 or more member rings, and (C) a photopolymerization initiator, (B)
  • the organosiloxane compound having a 6-membered or higher cyclic siloxane skeleton has a skeleton represented by the following general formula (1).
  • n represents an integer of 1 or more
  • (B) By combining an organosiloxane compound having a cyclic siloxane skeleton having a 6-membered ring or more, it is surprisingly possible to achieve both trade-off heat resistance and elongation. it can. Moreover, since halation is suppressed, the resolution is also good.
  • the alkali-soluble resin is a resin that contains one or more functional groups among phenolic hydroxyl groups, thiol groups, sulfo groups, and carboxyl groups, and is soluble in an alkaline solution, preferably two phenolic hydroxyl groups. Examples thereof include compounds having the above, carboxyl group-containing resins, compounds having phenolic hydroxyl groups and carboxyl groups, compounds having two or more thiol groups, and compounds having sulfo groups.
  • carboxyl group-containing resin is more preferable.
  • the carboxyl group-containing resin preferably has an ethylenically unsaturated group in the molecule in addition to the carboxyl group from the viewpoint of photocurability and development resistance, but the carboxyl group does not have an ethylenically unsaturated group. It may be a contained resin.
  • the ethylenically unsaturated group those derived from (meth) acrylic acid or derivatives thereof are preferable.
  • (meth) acrylic acid is a term that collectively refers to acrylic acid, methacrylic acid, and mixtures thereof, and the same applies to other similar expressions.
  • carboxyl group-containing resin examples include the compounds listed below (any of oligomers and polymers).
  • a carboxyl group-containing resin obtained by copolymerization of an unsaturated carboxylic acid such as (meth) acrylic acid and an unsaturated group-containing compound such as styrene, ⁇ -methylstyrene, lower alkyl (meth) acrylate, and isobutylene.
  • an unsaturated carboxylic acid such as (meth) acrylic acid
  • an unsaturated group-containing compound such as styrene, ⁇ -methylstyrene, lower alkyl (meth) acrylate, and isobutylene.
  • Diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, and aromatic diisocyanates; carboxyl group-containing dialcohol compounds such as dimethylolpropionic acid and dimethylolbutanoic acid, polycarbonate polyols, and polyethers
  • a carboxyl group-containing urethane resin by a polyaddition reaction of a diol compound such as a polyol, a polyester-based polyol, a polyolefin-based polyol, an acrylic polyol, a bisphenol A-based alkylene oxide adduct diol, a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group.
  • this carboxyl group-containing urethane resin has an aromatic ring, it is sufficient that at least one of diisocyanate, a carboxyl group-containing dialcohol compound and a diol compound has an aromatic
  • Diisocyanate compounds such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, polycarbonate polyols, polyether polyols, polyester polyols, polyolefin polyols, acrylic polyols, bisphenol A systems
  • a terminal carboxyl group-containing urethane resin obtained by reacting an acid anhydride with a terminal of a urethane resin by a polyaddition reaction of a diol compound such as an alkylene oxide adduct diol, a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group.
  • Diisocyanate and bifunctional epoxy resin such as bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bixylenol type epoxy resin, biphenol type epoxy resin
  • Photosensitive carboxyl group-containing urethane resin by polyaddition reaction of (meth) acrylate or its modified partial anhydride, carboxyl group-containing dialcohol compound and diol compound.
  • this photosensitive carboxyl group-containing urethane resin has an aromatic ring
  • at least one of diisocyanate, bifunctional epoxy resin (meth) acrylate or its partial acid anhydride modified product, carboxyl group-containing dialcohol compound and diol compound is aromatic. It only needs to have a ring.
  • one isocyanate group and one or more (meth) acryloyl groups are introduced into the molecule, such as an equimolar reaction product of isophorone diisocyanate and pentaerythritol triacrylate.
  • the carboxyl group-containing urethane resin which added the compound which has and was terminally (meth) acrylated When this photosensitive carboxyl group-containing urethane resin has an aromatic ring, a compound having one isocyanate group and one or more (meth) acryloyl groups in the molecule may have an aromatic ring.
  • a dibasic acid anhydride such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride
  • this photosensitive carboxyl group-containing resin has an aromatic ring, it is sufficient that at least one of a bifunctional epoxy resin and a dibasic acid anhydride has an aromatic ring.
  • a carboxyl group-containing polyester resin obtained by reacting a polyfunctional oxetane resin with a dicarboxylic acid and adding a dibasic acid anhydride to the resulting primary hydroxyl group.
  • this photosensitive carboxyl group-containing polyester resin has an aromatic ring, it is sufficient that at least one of a polyfunctional oxetane resin, dicarboxylic acid and dibasic acid anhydride has an aromatic ring.
  • Reaction product obtained by reacting a reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with an alkylene oxide such as ethylene oxide or propylene oxide, with an unsaturated group-containing monocarboxylic acid.
  • a carboxyl group-containing photosensitive resin obtained by reacting a product with a polybasic acid anhydride.
  • (11) Obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with a reaction product obtained by reacting a cyclic carbonate compound such as ethylene carbonate or propylene carbonate with an unsaturated group-containing monocarboxylic acid.
  • a carboxyl group-containing photosensitive resin obtained by reacting a reaction product with a polybasic acid anhydride.
  • An epoxy compound having a plurality of epoxy groups in one molecule a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule, such as p-hydroxyphenethyl alcohol, and (meth) Reacting with an unsaturated group-containing monocarboxylic acid such as acrylic acid, and then reacting with the alcoholic hydroxyl group of the resulting reaction product, maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, adipine A carboxyl group-containing photosensitive resin obtained by reacting a polybasic acid anhydride such as an acid.
  • this photosensitive carboxyl group-containing polyester resin has an aromatic ring, an epoxy compound, a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in a molecule, an unsaturated group-containing monocarboxylic acid and a polybasic It suffices that at least one of the acid anhydrides has an aromatic ring.
  • One epoxy group and one or more (meth) acryloyl groups in the molecule such as glycidyl (meth) acrylate, ⁇ -methylglycidyl (meth) acrylate and the like in any one of the resins (1) to (12) above
  • a photosensitive carboxyl group-containing resin obtained by adding a compound having a group.
  • this photosensitive carboxyl group-containing urethane resin has an aromatic ring
  • a compound having one epoxy group and one or more (meth) acryloyl groups in the molecule may have an aromatic ring.
  • a photosensitive carboxyl group-containing resin obtained by reacting a carboxyl group-containing (meth) acrylic copolymer resin with a compound having an oxirane ring and an ethylenically unsaturated group in one molecule.
  • Photosensitive carboxyl group-containing resin obtained by reacting a secondary hydroxyl group with a saturated or unsaturated polybasic acid anhydride.
  • the carboxyl group-containing resin as described above has a large number of carboxyl groups in the side chain of the backbone polymer, development with an alkaline aqueous solution becomes possible.
  • an alkali-soluble resin having at least one amideimide structure represented by the following formula (2) or (3) can also be suitably used.
  • a resin having an imide bond directly bonded to a cyclohexane ring or a benzene ring By including a resin having an imide bond directly bonded to a cyclohexane ring or a benzene ring, a cured product having higher toughness and heat resistance can be obtained.
  • the amide-imide resin having the structure represented by the following (2) is excellent in light transmittance, the resolution of the resin composition can be further improved.
  • the alkali-soluble resin having at least one amideimide structure represented by the following formula (2) or (3) preferably has transparency. For example, in a dry coating film of 25 ⁇ m, the transmittance of light having a wavelength of 365 nm is 70. % Or more is preferable. *
  • the content of the structures of the formulas (2) and (3) in the alkali-soluble resin having an amideimide structure is preferably 10 to 70% by mass.
  • a cured product having excellent solvent solubility and excellent physical properties such as heat resistance, tensile strength and elongation, and dimensional stability can be obtained.
  • the amount is preferably 10 to 60% by mass, more preferably 20 to 50% by mass.
  • alkali-soluble resin having an amideimide structure represented by the formula (2) in particular, the following formula (4A) or (4B) (In the formulas (4A) and (4B), R is a monovalent organic group, preferably H, CF 3 or CH 3 , and X is a direct bond or a divalent organic group,
  • R is a monovalent organic group, preferably H, CF 3 or CH 3
  • X is a direct bond or a divalent organic group
  • a resin having a structure represented by a bond, an alkylene group such as CH 2 or C (CH 3 ) 2 ) is preferable because it has excellent physical properties such as tensile strength and elongation and dimensional stability.
  • amideimide resin having the structure of the formula (2) a resin having a structure of the formulas (4A) and (4B) of 10 to 100% by mass can be suitably used. More preferably, it is 20 to 80% by mass.
  • an amideimide resin containing 5 to 100 mol% of the structures of the formulas (4A) and (4B) can be preferably used from the viewpoints of solubility and mechanical properties.
  • the amount is more preferably 5 to 98 mol%, further preferably 10 to 98 mol%, and particularly preferably 20 to 80 mol%.
  • the alkali-soluble resin having an amideimide structure represented by the formula (3) in particular, the formula (5A) or (5B) (In the formulas (5A) and (5B), R is a monovalent organic group, preferably H, CF 3 or CH 3 , X is a direct bond or a divalent organic group, It is preferable that the resin having a structure represented by a bond or an alkylene group such as CH 2 or C (CH 3 ) 2 is a cured product having excellent mechanical properties such as tensile strength and elongation. To preferred.
  • amideimide resin having the structure of the formula (3) a resin having a structure of the formulas (5A) and (5B) of 10 to 100% by mass can be suitably used. More preferably, it is 20 to 80% by mass.
  • an amideimide resin containing 2 to 95 mol% of the structure of the formulas (5A) and (5B) can also be preferably used because it exhibits good mechanical properties. More preferably, it is 10 to 80 mol%.
  • An alkali-soluble resin having an amideimide structure can be obtained by a known method.
  • the amidoimide resin having the structure of the formula (2) can be obtained using, for example, a diisocyanate compound having a biphenyl skeleton and a cyclohexane polycarboxylic acid anhydride.
  • diisocyanate compound having a biphenyl skeleton examples include 4,4′-diisocyanate-3,3′-dimethyl-1,1′-biphenyl and 4,4′-diisocyanate-3,3′-diethyl-1,1′-biphenyl.
  • 4,4'-diisocyanate-2,2'-dimethyl-1,1'-biphenyl, 4,4'-diisocyanate-2,2'-diethyl-1,1'-biphenyl, 4,4'-diisocyanate- Examples include 3,3′-ditrifluoromethyl-1,1′-biphenyl, 4,4′-diisocyanate-2,2′-ditrifluoromethyl-1,1′-biphenyl, and the like.
  • aromatic polyisocyanate compounds such as diphenylmethane diisocyanate may be used.
  • cyclohexane polycarboxylic acid anhydride examples include cyclohexane tricarboxylic acid anhydride and cyclohexane tetracarboxylic acid anhydride.
  • the amidoimide resin having the structure of the formula (3) can be obtained by using, for example, the diisocyanate compound having the biphenyl skeleton and the polycarboxylic acid anhydride having two acid anhydride groups.
  • polycarboxylic acid anhydrides having two acid anhydride groups examples include pyromellitic dianhydride, benzophenone-3,3 ′, 4,4′-tetracarboxylic dianhydride, diphenyl ether-3,3 ′, 4,4′-tetracarboxylic dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, biphenyl-3,3 ′, 4,4′-tetracarboxylic dianhydride, biphenyl- 2,2 ′, 3,3′-tetracarboxylic dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, 1,1 -Bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, 2,2-bis
  • alkali-soluble resin having the amideimide structure examples include Unidic V-8000 series manufactured by DIC and SOXR-U manufactured by Nippon Kogyo Paper Industries.
  • the acid value of the alkali-soluble resin is preferably in the range of 20 to 120 mgKOH / g, more preferably in the range of 30 to 100 mgKOH / g.
  • the weight average molecular weight of the (A) alkali-soluble resin of the resin composition of the present invention varies depending on the resin skeleton, but is generally preferably 2,000 to 150,000. When the weight average molecular weight is 2,000 or more, the tack-free property of the dried coating film, the moisture resistance of the coating film after exposure are good, and the resolution is also better. On the other hand, when the weight average molecular weight is 150,000 or less, developability and storage stability are good. More preferably, it is 5,000 to 100,000.
  • (B) Organosiloxane compound having a cyclic siloxane skeleton having 6 or more member rings (B) As an organosiloxane compound having a cyclic siloxane skeleton having a 6-membered ring or more (hereinafter also referred to as “(B) organosiloxane compound”), a cyclic siloxane having a 6-membered ring or more represented by the following general formula (1) A known and conventional compound having a skeleton may be used.
  • n represents an integer of 1 or more
  • the cyclic siloxane skeleton is preferably a 6 to 12 membered ring (ie, n in the general formula (1) is an integer of 1 to 4), and the 6 to 8 membered ring (ie, n in the general formula (1) is More preferably 1 or 2).
  • the organosiloxane compound preferably has a thermosetting reactive group.
  • thermosetting reactive groups include hydroxyl groups, carboxyl groups, isocyanate groups, amino groups, imino groups, epoxy groups, oxetanyl groups, mercapto groups, methoxymethyl groups, methoxyethyl groups, ethoxymethyl groups, ethoxyethyl groups, oxazoline groups, etc. Is mentioned.
  • an epoxy group is preferable.
  • the number of functional groups of the thermosetting reactive group is preferably 1 to 6, more preferably 1 to 4.
  • the organosiloxane compound may have a photosensitive group.
  • a photosensitive group is preferred because bleeding can be prevented.
  • the photosensitive group include ethylenically unsaturated groups such as a vinyl group, a styryl group, a methacryl group, and an acrylic group. Among these, a vinyl group, a styryl group, a methacryl group, and an acrylic group are preferable.
  • the number of functional groups of the photosensitive group is preferably 1 to 6, and more preferably 1 to 4.
  • the organosiloxane compound may have both a thermosetting reactive group and a photosensitive group. When both are provided, it is possible to achieve a well-balanced improvement in heat resistance, adhesion, and prevention of bleeding.
  • thermosetting reactive group and the photosensitive group is preferably bonded directly or via an organic group to the Si atom of the 6-membered or higher cyclic siloxane skeleton represented by the general formula (1).
  • the organic group may be branched, may have a substituent such as a hydroxyl group, and may be interrupted by an oxygen atom, a sulfur atom, a carbonyl group, an ester group, or the like.
  • the organic group preferably has 1 to 10 carbon atoms, and more preferably 2 to 8 carbon atoms.
  • organosiloxane compounds include X-40-2670 and X-40-2678 manufactured by Shin-Etsu Silicone, CX-783 manufactured by DMI, 1,3,5-trivinyl-1, manufactured by Wako Pure Chemical Industries, Ltd. 3,5-trimethylcyclotrisiloxane and the like.
  • organosiloxane compound examples include the following compounds, but are not limited thereto.
  • the blending amount of the (B) organosiloxane compound is 1 to 200 parts by mass, and more preferably 5 to 100 parts by mass with respect to 100 parts by mass of the (A) alkali-soluble resin.
  • photopolymerization initiator Any photopolymerization initiator may be used as long as it is a known photopolymerization initiator as a photopolymerization initiator or a photoradical generator.
  • (C) As the photopolymerization initiator, for example, bis- (2,6-dichlorobenzoyl) phenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -2,5-dimethylphenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -4-propylphenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -1-naphthylphosphine oxide, bis- (2,6-dimethoxybenzoyl) phenylphosphine oxide, Bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,5-dimethylphenylphosphine oxide, bis- (2,4 , 6-Trimethylbenzoyl) -phenylphosphine Bisacylphosphin
  • the blending amount of the photopolymerization initiator is preferably 0.01 to 50 parts by mass and more preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the (A) alkali-soluble resin in terms of solid content.
  • the negative photocurable resin composition of the present invention can contain a compound having an ethylenically unsaturated group.
  • a compound having an ethylenically unsaturated group when the components (A) to (C) have an ethylenically unsaturated group, such a compound is excluded from the “compound having an ethylenically unsaturated group”.
  • photopolymerizable oligomers As the compound having an ethylenically unsaturated group, known and commonly used photopolymerizable oligomers, photopolymerizable vinyl monomers, and the like are used.
  • examples of the photopolymerizable oligomer include unsaturated polyester oligomers and (meth) acrylate oligomers.
  • Examples of (meth) acrylate oligomers include phenol novolac epoxy (meth) acrylate, cresol novolac epoxy (meth) acrylate, epoxy (meth) acrylates such as bisphenol type epoxy (meth) acrylate, urethane (meth) acrylate, epoxy urethane (meta ) Acrylate, polyester (meth) acrylate, polyether (meth) acrylate, polybutadiene-modified (meth) acrylate, and the like.
  • photopolymerizable vinyl monomer known and commonly used monomers, for example, styrene derivatives such as styrene, chlorostyrene and ⁇ -methylstyrene; vinyl esters such as vinyl acetate, vinyl butyrate or vinyl benzoate; vinyl isobutyl ether, vinyl- vinyl ethers such as n-butyl ether, vinyl-t-butyl ether, vinyl-n-amyl ether, vinyl isoamyl ether, vinyl-n-octadecyl ether, vinyl cyclohexyl ether, ethylene glycol monobutyl vinyl ether, triethylene glycol monomethyl vinyl ether; acrylamide, Methacrylamide, N-hydroxymethylacrylamide, N-hydroxymethylmethacrylamide, N-methoxymethylacrylamide, N-ethoxymethylacrylamide (Meth) acrylamides such as rilamide and N-butoxymethylacrylamide; allyl compounds such as triallyl isocyan
  • the compound having an ethylenically unsaturated group is preferably a compound having a (meth) acryloyl group, that is, a (meth) acrylate compound.
  • a (meth) acrylate compound becomes more heat resistant, it is preferable that it is bifunctional or more.
  • the (meth) acrylate compound is preferable when the acrylic equivalent is 100 or more because the elongation becomes better, the halation is further suppressed, and the warpage of the cured product hardly occurs.
  • R 1 is a hydrogen atom or an organic group having 1 to 20 carbon atoms, which may be the same or different
  • R 2 is an alkyl group having 1 to 10 carbon atoms, an alkylene group having 1 to 10 carbon atoms, And at least one functional group selected from the group consisting of phenylene groups
  • R 3 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
  • R 4 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
  • R 5 represents a hydrogen atom or a methyl group
  • p represents an integer of 1 to 5
  • q represents an integer of 3 or more
  • m represents an integer of 1 to 4
  • n represents an integer of 1 to 10.
  • the (meth) acrylate compound comprises (a) a hydroxyl group formed by reacting (b) a cyclic ether compound or a cyclic carbonate compound with a compound having three or more phenolic hydroxyl groups in one molecule.
  • the compound (a) having three or more phenolic hydroxyl groups in one molecule is a compound having a phenolic hydroxyl group having a softening point of room temperature or higher, and the ethylenically unsaturated group.
  • the compound (c) having a methacrylic acid is preferably methacrylic acid.
  • the compound having an ethylenically unsaturated group one type may be used alone, or two or more types may be used in combination.
  • the compounding amount of the compound having an ethylenically unsaturated group is 1 to 80 parts by mass, more preferably 2 to 70 parts by mass with respect to 100 parts by mass of the (A) alkali-soluble resin.
  • thermosetting component The negative photocurable resin composition of the present invention can contain a thermosetting component. By further thermosetting the photocured composition, it is possible to improve properties such as heat resistance and insulation reliability of the cured product.
  • thermosetting component known and commonly used thermosetting resins such as amino resins, melamine resins, maleimide compounds, benzoxazine resins, carbodiimide resins, cyclocarbonate compounds, epoxy compounds, polyfunctional oxetane compounds, and episulfide resins can be used.
  • an epoxy compound, an oxetane compound, and a maleimide compound can be suitably used, and these may be used in combination.
  • epoxy compound known and commonly used compounds having one or more epoxy groups can be used, and among them, compounds having two or more epoxy groups are preferable.
  • monoepoxy compounds such as butyl glycidyl ether, phenyl glycidyl ether, glycidyl (meth) acrylate, bisphenol A type epoxy resin, bisphenol S type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin , Cycloaliphatic epoxy resin, trimethylolpropane polyglycidyl ether, phenyl-1,3-diglycidyl ether, biphenyl-4,4′-diglycidyl ether, 1,6-hexanediol diglycidyl ether, ethylene glycol or propylene glycol Diglycidyl ether, sorbitol polyglycidyl ether, tris (2,3-epoxypropyl) isocyanurate, trigly
  • the compound having two or more epoxy groups include jER828, jER834, jER1001, jER1004 manufactured by Mitsubishi Chemical Corporation, Epicron 840, Epicron 850, Epicron 1050, Epicron 1050, Epicron 2055, Nippon Steel & Sumikin Chemical Co., Ltd. Epototo YD-011, YD-013, YD-127, YD-128 manufactured by Dow Chemical Japan Co., Ltd. E. R. 317, D.E. E. R. 331, D.D. E. R. 661, D.D. E. R. 664, Sumi-epoxy ESA-011, ESA-014, ELA-115, ELA-128 manufactured by Sumitomo Chemical Co., Ltd. E. R.
  • Brominated epoxy resins such as 714; jER152 and jER154 manufactured by Mitsubishi Chemical Corporation, and D.C. E. N. 431, D.D. E. N. 438, Epicron N-730, Epicron N-770, Epicron N-865 manufactured by DIC, Epototo YDCN-701, YDCN-704 manufactured by Nippon Steel & Sumikin Chemical Co., EPPN-201, EOCN-1025 manufactured by Nippon Kayaku Co., Ltd.
  • ECN-235 ECN-299, YDCN-700-2, YDCN-700-3, YDCN-700-5, YDCN-700-7, YDCN-700-10, YDCN-704 YDCN-704A manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.
  • EPX-30 manufactured by ADEKA, EXA-1514 manufactured by DIC, etc .
  • Bisphenol A novolac type epoxy resin such as jER157S manufactured by Mitsubishi Chemical Co., Ltd .
  • Tetraphenylolethane type epoxy resin such as jERYL-931
  • heterocyclic epoxy resin such as TEPIC manufactured by Nissan Chemical Industries
  • diglycidyl phthalate resin such as Bremer DGT manufactured by Nippon Oil Corporation
  • ZX-1063 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.
  • Tetraglycidylxylenoyl Tan resin Epoxy resins containing naphthalene groups such as ESN-190, ESN-360 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., HP-4032, EXA-4750, EXA-4700 manufactured by DIC, etc .; HP-7200, HP-7200H manufactured by DIC, etc.
  • Epoxy resin having dicyclopentadiene skeleton Epoxy resin having dicyclopentadiene skeleton; glycidyl methacrylate copolymer epoxy resin such as CP-50S, CP-50M manufactured by NOF Corporation; copolymer epoxy resin of cyclohexylmaleimide and glycidyl methacrylate; CTBN-modified epoxy resin (for example, And YR-102, YR-450 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), etc., but are not limited thereto.
  • oxetane compound containing an oxetane ring represented by (wherein R 6 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms) include 3-ethyl-3-hydroxymethyloxetane (Toagogi).
  • OXT-101 3-ethyl-3- (phenoxymethyl) oxetane (OXT-211 manufactured by Toagosei Co., Ltd.), 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane (OXT manufactured by Toagosei Co., Ltd.) -212), 1,4-bis ⁇ [(3-ethyl-3-oxetanyl) methoxy] methyl ⁇ benzene (OXT-121 manufactured by Toagosei Co., Ltd.), bis (3-ethyl-3-oxetanylmethyl) ether (Toagosei) OXT-221) manufactured by the company. Furthermore, phenol novolac type oxetane compounds and the like can also be mentioned. The oxetane compound may be used in combination with the above epoxy compound or may be used alone.
  • maleimide compound examples include polyfunctional aliphatic / alicyclic maleimide and polyfunctional aromatic maleimide. Bifunctional or higher maleimide compounds (polyfunctional maleimide compounds) are preferred.
  • polyfunctional aliphatic / alicyclic maleimide examples include N, N′-methylene bismaleimide, N, N′-ethylene bismaleimide, tris (hydroxyethyl) isocyanurate, and aliphatic / alicyclic maleimide carboxylic acid.
  • Maleimides isophorone bisurethane bis (N-ethylmaleimide), triethylene glycol bis (maleimide ethyl carbonate), aliphatic / alicyclic maleimide carboxylic acid and various aliphatic / alicyclic polyols, or dehydrated ester
  • aromatic polymaleimide ester compounds obtained by dehydrating esterification of maleimide carboxylic acid and various aromatic polyols, or transesterification reaction of maleimide carboxylic acid ester and various aromatic polyols; Aromatic polymaleimide ester compounds obtained by ether ring-opening reaction of carboxylic acid and various aromatic polyepoxides; Aromatic polymaleimide urethane compounds obtained by urethanization reaction of maleimide alcohol and various aromatic polyisocyanates, etc. And aromatic polyfunctional maleimides.
  • a liquid polyfunctional maleimide is preferable because the elongation percentage is better.
  • the liquid polyfunctional maleimide means a polyfunctional maleimide whose viscosity at 60 ° C. and 5 rpm is measured with a cone plate viscometer (TVH-33H manufactured by Toki Sangyo Co., Ltd.) and is 50,000 cp or less. .
  • thermosetting component may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the blending amount of the thermosetting component is preferably 0.1 to 100 parts by mass, more preferably 0.5 to 100 parts by mass with respect to 100 parts by mass of the alkali-soluble resin (A) in terms of solid content, and 1 to 60 parts by mass. Part is more preferred.
  • the blending amount of the maleimide compound is preferably 0.1 to 50 parts by weight, more preferably 0.00, based on 100 parts by weight of the (A) alkali-soluble resin in terms of solid content. 2 to 20 parts by mass.
  • the blending amount of the maleimide compound is in the range of 0.1 to 50 parts by mass, the balance between high elongation and heat resistance is excellent.
  • thermosetting catalyst The negative photocurable resin composition of the present invention can contain a thermosetting catalyst.
  • the thermosetting catalyst include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- Imidazole derivatives such as (2-cyanoethyl) -2-ethyl-4-methylimidazole; dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzyl Amine, amine compounds such as 4-methyl-N, N-dimethylbenzylamine, hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide; phosphorus compounds such as triphenylphos
  • Examples of commercially available products include 2MZ-AP, 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (both trade names of imidazole compounds) manufactured by Shikoku Kasei Kogyo Co., Ltd. -CAT3503N, U-CAT3502T (all are trade names of blocked isocyanate compounds of dimethylamine), DBU, DBN, U-CATSA102, U-CAT5002 (all are bicyclic amidine compounds and salts thereof), and the like.
  • the present invention is not limited to these, and any epoxy compound or oxetane compound thermosetting catalyst or other thermosetting component may be used. You can use it.
  • the blending amount of the thermosetting catalyst is preferably 0.1 to 20 parts by mass, more preferably 0.2 to 20 parts by mass with respect to 100 parts by mass of the (A) alkali-soluble resin in terms of solid content.
  • the blending amount of the thermosetting catalyst is in the range of 0.1 to 20 parts by mass, the balance between storage stability and curability is excellent.
  • the negative photocurable resin composition of the present invention preferably contains a polymerization inhibitor and can further suppress halation.
  • the polymerization inhibitor is not particularly limited, and a photopolymerization inhibitor and a thermal polymerization inhibitor can be used.
  • photopolymerization inhibitors include p-benzoquinone, naphthoquinone, di-t-butyl paracresol, hydroquinone monomethyl ether, ⁇ -naphthol, acetamidine acetate, hydrazine hydrochloride, trimethylbenzylammonium chloride, dinitrobenzene, picric acid Quinone dioxime, pyrogallol, tannic acid, resorzine, cuperone, phenothiazine, and the like.
  • thermal polymerization inhibitors include 4-methoxyphenol, hydroquinone, alkyl or aryl-substituted hydroquinone, t-butylcatechol, pyrogallol, 2-hydroxybenzophenone, 4-methoxy-2-hydroxybenzophenone, cuprous chloride, phenothiazine, chloranil, Naphthylamine, ⁇ -naphthol, 2,6-di-t-butyl-4-cresol, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), pyridine, nitrobenzene, dinitrobenzene, picric acid, 4- Toluidine, methylene blue, copper and organic chelating agent reactant, methyl salicylate, and phenothiazine, nitroso compound, chelate of nitroso compound and Al, and the like.
  • the polymerization inhibitor is preferably a photopolymerization inhibitor, and quinone-based photopolymerization inhibitors such as p-benzoquinone, naphthoquinone, hydroquinone monomethyl ether, and quinonedioxime are particularly preferable.
  • a polymerization inhibitor may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the blending amount of the polymerization inhibitor is 0.005 to 20 parts by mass, more preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the (A) alkali-soluble resin.
  • the negative photocurable resin composition of the present invention can contain a leveling agent.
  • the leveling agent is not particularly limited.
  • a polyacrylate polymer a polyether-modified dimethylpolysiloxane copolymer, a polyester-modified dimethylpolysiloxane copolymer, a polyether-modified methylalkylpolysiloxane copolymer, and an aralkyl-modified polymer.
  • a polyacrylate polymer a polyether-modified dimethylpolysiloxane copolymer, a polyester-modified dimethylpolysiloxane copolymer, a polyether-modified methylalkylpolysiloxane copolymer, and an aralkyl-modified polymer.
  • examples thereof include a methyl alkyl polysiloxane copolymer and a polyether-modified methyl alkyl polysiloxane copolymer.
  • leveling agents examples include BYK-350, -352, -354, -356, -361N, -392 manufactured by Big Chemie Japan, and Polyflow series manufactured by Kyoeisha Chemical.
  • a leveling agent may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the blending amount of the leveling agent is 0.005 to 20 parts by mass, more preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the (A) alkali-soluble resin.
  • the negative photocurable resin composition of the present invention can contain a colorant.
  • the colorant is not particularly limited, and conventionally known colorants such as red, blue, green, yellow, white and black can be used, and any of pigments, dyes and pigments may be used. Specific examples include color index (CI; issued by The Society of Dyer's and Colorists) number. However, it is preferable that the colorant does not contain a halogen from the viewpoint of reducing environmental burden and affecting the human body.
  • red colorant examples include monoazo, diazo, azo lake, benzimidazolone, perylene, diketopyrrolopyrrole, condensed azo, anthraquinone, and quinacridone.
  • blue colorants include metal-substituted or unsubstituted phthalocyanine-based and anthraquinone-based compounds, and pigment-based compounds that are classified as pigments.
  • the green colorant includes metal-substituted or unsubstituted phthalocyanine-based, anthraquinone-based, and perylene-based materials.
  • yellow colorants include monoazo, disazo, condensed azo, benzimidazolone, isoindolinone, and anthraquinone.
  • white colorant examples include rutile type, anatase type titanium oxide and the like.
  • Black colorants include titanium black, carbon black, graphite, iron oxide, anthraquinone, cobalt oxide, copper oxide, manganese, antimony oxide, nickel oxide, perylene, and aniline. Examples thereof include pigments, molybdenum sulfide, and bismuth sulfide.
  • a colorant such as purple, orange or brown may be added for the purpose of adjusting the color tone.
  • Coloring agents can be used alone or in combination of two or more. Although the compounding quantity of a coloring agent is not specifically limited, It is preferable to set it as 10 mass parts or less with respect to 100 mass parts of (A) alkali-soluble resin. More preferably, it is 0.1 to 5 parts by mass.
  • the negative photocurable resin composition of the present invention can contain an organic solvent for the purpose of preparing the composition and adjusting the viscosity when applied to a substrate or a carrier film.
  • organic solvents include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether , Glycol ethers such as dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, diethylene glycol monomethyl ether acetate, tripropylene glycol monomethyl ether; ethyl acetate, butyl acetate, butyl lactate, cellosolve acetate, butyl cellosolve acetate, carbit
  • the negative type photocurable resin composition of the present invention may be blended with other known and commonly used additives in the field of electronic materials.
  • additives include antioxidants, UV absorbers, silane coupling agents, plasticizers, flame retardants, antistatic agents, anti-aging agents, antibacterial / antifungal agents, antifoaming agents, organic fillers, inorganic fillers, Thickener, adhesion promoter, thixotropic agent, photoinitiation aid, sensitizer, curing accelerator, mold release agent, surface treatment agent, dispersant, wetting dispersant, dispersion aid, surface modifier , Stabilizers, phosphors and the like.
  • the negative photocurable resin composition of the present invention may be used as a dry film or as a liquid. When used as a liquid, it may be one-component or two-component or more.
  • the organosiloxane compound has a thermosetting reactive group, it is preferable to separate the thermosetting catalyst into two or more liquids from the viewpoint of stability during storage. Moreover, when (B) organosiloxane compound has a photosensitive group, it is preferable to make it into 2 liquids or more separately from a photoinitiator.
  • the dry film of the present invention has a resin layer obtained by applying and drying the negative photocurable resin composition of the present invention on a carrier film.
  • the negative photocurable resin composition of the present invention is diluted with the above organic solvent and adjusted to an appropriate viscosity, and then a comma coater, a blade coater, a lip coater, and a rod coater are used.
  • the squeeze coater, reverse coater, transfer roll coater, gravure coater, spray coater, etc. are used to apply a uniform thickness on the carrier film.
  • the applied composition is usually dried at a temperature of 50 to 130 ° C. for 1 to 30 minutes to form a resin layer.
  • the coating film thickness is not particularly limited, but in general, the film thickness after drying is appropriately selected in the range of 10 to 150 ⁇ m, preferably 20 to 60 ⁇ m.
  • a plastic film is used as the carrier film.
  • a polyester film such as polyethylene terephthalate (PET), a polyimide film, a polyamideimide film, a polypropylene film, a polystyrene film, or the like can be used.
  • the thickness of the carrier film is not particularly limited, but is generally appropriately selected within the range of 10 to 150 ⁇ m.
  • the film surface can be further peeled off for the purpose of preventing dust from adhering to the film surface. It is preferable to laminate a cover film.
  • a cover film for example, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a surface-treated paper, or the like can be used.
  • a cover film what is necessary is just a thing smaller than the adhesive force of a resin layer and a carrier film when peeling a cover film.
  • the negative photocurable resin composition of the present invention is applied on the cover film and dried to form a resin layer, and a carrier film is laminated on the surface.
  • a carrier film is laminated on the surface.
  • the resin layer obtained after applying the composition and evaporating and drying the solvent is exposed.
  • the exposed portion light irradiated portion
  • the exposed portion is cured.
  • exposure is selectively performed with an active energy ray through a photomask having a pattern formed by a contact method or a non-contact method, or direct pattern exposure is performed by a laser direct exposure machine, and an unexposed portion is subjected to an alkaline aqueous solution (for example, The resist pattern is formed by development with a 0.3 to 3 mass% sodium carbonate aqueous solution.
  • a cured film (cured product) with excellent properties such as heat resistance, chemical resistance, moisture absorption resistance, adhesion, and electrical properties. ) Can be formed.
  • the composition When using the negative photocurable resin composition of the present invention as a photocurable resin composition, the composition is applied, the solvent is evaporated and dried, and exposure (light irradiation) is performed, thereby exposing the exposed portion.
  • a cured film (cured product) can be formed by curing the (irradiated portion).
  • the negative photocurable resin composition of the present invention is prepared, for example, by adjusting the viscosity to be suitable for the coating method using the organic solvent, and applying the dip coating method, flow coating method, roll coating method, bar coating on the substrate. After coating by the coater method, screen printing method, curtain coating method, etc., the organic solvent contained in the composition is evaporated and dried (temporary drying) at a temperature of about 60-100 ° C. Can be formed. In the case of a dry film obtained by applying the above composition on a carrier film or a cover film and drying and winding it as a film, the layer of the composition of the present invention is brought into contact with the substrate by a laminator or the like. After bonding together, the resin layer can be formed by peeling off the carrier film.
  • Examples of the base material include printed wiring boards and flexible printed wiring boards that have been previously formed with copper or the like, paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth / non-woven cloth epoxy, glass cloth / paper epoxy.
  • PEN polyethylene naphthalate
  • the volatile drying or thermal curing may be performed by a hot air circulation drying furnace, an IR furnace, a hot plate, a convection oven or the like (a method and nozzle in which hot air in a dryer is brought into countercurrent contact using a steam-heated type heat source. And a method of spraying on a support.
  • the exposure apparatus used for the active energy ray irradiation may be any apparatus that irradiates ultraviolet rays in the range of 350 to 450 nm, equipped with a high-pressure mercury lamp lamp, an ultra-high pressure mercury lamp lamp, a metal halide lamp, a mercury short arc lamp, etc.
  • a direct drawing apparatus for example, a laser direct imaging apparatus that directly draws an image with a laser using CAD data from a computer
  • the lamp light source or laser light source of the direct drawing machine may have a maximum wavelength in the range of 350 to 410 nm.
  • the exposure amount for image formation varies depending on the film thickness and the like, but can be generally in the range of 20 to 1000 mJ / cm 2 , preferably 20 to 800 mJ / cm 2 .
  • the developing method can be a dipping method, a shower method, a spray method, a brush method, etc., and as a developing solution, potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, Alkaline aqueous solutions such as ammonia and amines can be used.
  • the negative photocurable resin composition of the present invention is useful for forming a pattern layer as a permanent film of a printed wiring board such as a solder resist, a cover lay, and an interlayer insulating layer, particularly for forming an interlayer insulating layer. Useful. Further, since the negative photocurable resin composition of the present invention is excellent in resolution, the pattern layer of an IC package that is required to form a fine pattern, particularly FOWLP (Fan-Out Wafer Level Package) or PLP (PLP). It can also be suitably used for forming a redistribution layer of (Panel Level Package).
  • the negative photocurable resin composition of the present invention is excellent in resolution, heat resistance, and elongation even when cured at a low temperature of 200 ° C. or lower, so that high temperature processing is difficult, for example, in the manufacture of IC packages. The adverse effect on the material can be suppressed.
  • the number average molecular weight was 934 in terms of polystyrene, and the weight average molecular weight was 1420 in terms of polystyrene.
  • the acid value was 63.2 KOH-mg / g (in terms of solid content).
  • the number average molecular weight was 1084 in terms of polystyrene, and the weight average molecular weight was 1524 in terms of polystyrene.
  • the acid value was 68.3 KOH-mg / g (in terms of solid content).
  • reaction solution was cooled to room temperature, and 1.56 g of 89% phosphoric acid was added to and mixed with the reaction solution to neutralize potassium hydroxide.
  • the nonvolatile content was 62.1% and the hydroxyl value was 182.2 g / eq.
  • a novolak-type cresol resin propylene oxide reaction solution was obtained. This was an average of 1.08 moles of alkylene oxide added per equivalent of phenolic hydroxyl group.
  • reaction solution was washed with 5% NaCl aqueous solution, toluene was distilled off with an evaporator, and carbitol acetate was added to obtain a resin solution of a phenol starting alkylene oxide modified acrylate having a solid content of 70%. .
  • Examples 1 to 15, Comparative Example 1 In accordance with the formulation shown in Tables 1 and 2 below, each component was blended, premixed with a stirrer, dispersed with a three-roll mill, and kneaded to prepare curable resin compositions. In addition, the compounding quantity in a table
  • A-DCP (bifunctional; tricyclodecane dimethanol diacrylate; molecular weight 304) * 14: BASF Japan-made Laromar LR8863 (trifunctional; ethylene oxide-added trimethylolpropane triacrylate; molecular weight of about 340) * 15: UN9200A manufactured by Negami Kogyo Co., Ltd. (bifunctional: polycarbonate urethane acrylate having a non-aromatic polycarbonate skeleton; molecular weight 15000) * 16: Dipentaerythritol hexaacrylate (hexafunctional; molecular weight 578; acrylic equivalent less than 100) * 17: Shin-Nakamura Chemical Co., Ltd.
  • A-TMPT trifunctional; trimethylolpropane triacrylate; molecular weight 296; acrylic equivalent less than 100
  • 18 Osaka Organic Chemical Co., Ltd.
  • IBXA monofunctional; isobornyl acrylate; molecular weight 208; acrylic equivalent 208) * 19: Resin solution of phenol-started alkylene oxide modified acrylate synthesized in Synthesis Example 6 (solid content: 70%) * 20: BMI-1500 (design bismaleimide: bismaleimide oligomer, 60 ° C., cone cone viscometer (TVH-33H, Toki Sangyo Co., Ltd.) at 5 rpm) 20,000 ⁇ 10 , 000 cp) * 21: HP-7200L manufactured by DIC (alicyclic epoxy compound; diluted product of carbitol acetate, solid content 85%) * 22: X-40-2670 (tetrafunctional alicyclic epoxy compound having a cyclic organosiloxane 8-membered ring
  • Tg Heat resistance (glass transition temperature Tg) Tg was measured by the DMA method in accordance with IPC TM-650 under conditions of a heating rate of 5 ° C./min and a tensile mode. Tg of 190 ° C. or higher was rated as “ ⁇ ”, less than 190 ° C. of 180 ° C. or higher as ⁇ , lower than 180 ° C. of 170 ° C. or higher as ⁇ , and lower than 170 ° C. as X.
  • the elongation rate (tensile elongation at break) was measured using a tensile tester (AGS-G100W manufactured by Shimadzu Corporation) under the conditions of a tensile speed of 1.0 mm / min and 23 ° C. in accordance with JISK7127.
  • a resist was formed to a thickness of 20 ⁇ m on a 35 ⁇ m-thick copper foil, and evaluation was performed based on the total amount of warpage of the four corners after curing in a predetermined process.
  • the total is 20 mm or more and less than 25 mm, ⁇ , 25 mm or more and less than 30 mm is given as ⁇ , and 30 mm or more is taken as x.
  • the obtained silicon wafer for evaluation was irradiated with ultraviolet rays under a condition of an integrated exposure amount of 1000 mJ / cm 2 in a UV conveyor furnace, and then cured by heating at 180 ° C. for 60 minutes.
  • the resist coating thickness is 10 to 15 ⁇ m
  • the designed opening diameter is 20 ⁇ m
  • the actually measured value is 20 to 19 ⁇ m, that is, the halation is within 1 ⁇ m.
  • ⁇ was obtained when the halation was more than 1 ⁇ m and 2 ⁇ m or less, and x was given when the halation was more than 2 ⁇ m.
  • the negative photocurable resin composition of the present invention is excellent in resolution and can form a cured product having high heat resistance and high elongation.

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Abstract

La présente invention porte sur : une composition de résine photodurcissable négative qui est apte à former un produit durci présentant une excellente résolution, une résistance à la chaleur élevée et un allongement élevé ; un film sec qui a une couche de résine qui est obtenue à partir de ladite composition ; un produit durci de ce film sec ; et une carte de câblage imprimé qui comprend ce produit durci. L'invention concerne une composition de résine photodurcissable négative qui est caractérisée en ce qu'elle comprend (A) une résine soluble en milieu alcalin, (B) un composé organosiloxane présentant un squelette siloxane cyclique ayant au moins 6 chaînons de cycle et (C) un initiateur de photopolymérisation, et qui est également caractérisé en ce que le composé organosiloxane (B) présentant un squelette siloxane cyclique ayant au moins 6 chaînons de cycle présente un squelette représenté par la formule générale (1). (Dans la formule, n représente un nombre entier supérieure ou égal à 1.)
PCT/JP2017/046022 2016-12-28 2017-12-21 Composition de résine photodurcissable négative, film sec, produit durci et carte de câblage imprimée WO2018123826A1 (fr)

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JP2016151748A (ja) * 2015-02-19 2016-08-22 日立化成株式会社 感光性導電フィルム、それを用いた導電パターンの形成方法、導電パターン基板及びタッチパネルセンサ
JP2017171748A (ja) * 2016-03-22 2017-09-28 Jsr株式会社 硬化膜、表示素子、硬化膜形成用材料及び硬化膜の形成方法
JP2018005231A (ja) * 2016-06-29 2018-01-11 奇美實業股▲分▼有限公司 ネガ型感光性樹脂組成物、スペーサの製造方法、保護膜の製造方法、および液晶表示素子
JP2018004920A (ja) * 2016-06-30 2018-01-11 東京応化工業株式会社 感光性樹脂組成物、硬化膜、有機ｅｌ素子における発光層の区画用のバンク、有機ｅｌ素子用の基板、有機ｅｌ素子、硬化膜の製造方法、バンクの製造方法、及び有機ｅｌ素子の製造方法

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