WO2020202691A1 - Composition de résine photosensible, film sec, produit durci, et composant électronique - Google Patents

Composition de résine photosensible, film sec, produit durci, et composant électronique Download PDF

Info

Publication number
WO2020202691A1
WO2020202691A1 PCT/JP2020/000762 JP2020000762W WO2020202691A1 WO 2020202691 A1 WO2020202691 A1 WO 2020202691A1 JP 2020000762 W JP2020000762 W JP 2020000762W WO 2020202691 A1 WO2020202691 A1 WO 2020202691A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
photosensitive resin
resin composition
silica
maleimide
Prior art date
Application number
PCT/JP2020/000762
Other languages
English (en)
Japanese (ja)
Inventor
沙和子 嶋田
千穂 植田
知哉 工藤
将太郎 種
岡田　和也
Original Assignee
太陽インキ製造株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 太陽インキ製造株式会社 filed Critical 太陽インキ製造株式会社
Publication of WO2020202691A1 publication Critical patent/WO2020202691A1/fr

Links

Classifications

    • 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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings

Definitions

  • the present invention relates to a photosensitive resin composition, a dry film, a cured product, and an electronic component.
  • an object of the present invention is to obtain a photosensitive resin composition having excellent reliability such as heat resistance and crack resistance, and having excellent light characteristics (resolution), from the composition. It is an object of the present invention to provide a dry film having a resin layer, a cured product of the composition or the resin layer of the dry film, and an electronic component having the cured product.
  • the present inventors have cured with a repeating unit derived from a maleimide-based monomer and a repeating unit derived from an unsaturated carboxylic acid ester monomer having a heat-crosslinkable group. Obtained by blending a sex copolymer resin, an epoxy resin, a maleimide compound having two or more maleimide structures in one molecule, a photopolymerization initiator, and a specific amount of silica, and subjecting the mixture to light irradiation and heat treatment at 160 ° C. Difference (HL) between the average linear thermal expansion rate (L) calculated in the range of 0 ° C. to 50 ° C. and the average linear thermal expansion coefficient (H) calculated in the range of 200 ° C. to 250 ° C. It has been found that the above-mentioned problems can be solved by having a specific range, and the present invention has been completed.
  • HL Difference between the average linear thermal expansion rate (L) calculated in the range of 0 ° C. to 50 °
  • the photosensitive resin composition of the present invention has (A) at least a first repeating unit represented by the following formula (1) and a second repeating unit represented by the following formula (2).
  • the amount of the silica (D) blended is 25 to 75% by mass based on the total solid content of the photosensitive resin composition, and the photosensitive resin composition is irradiated with light of 1000 mJ / cm 2 and 160 ° C. for 1 hour.
  • the photosensitive resin composition of the present invention preferably has a weight average molecular weight of the curable copolymer resin (A) of less than 10,000.
  • the photosensitive resin composition of the present invention contains two or more of the (B1) epoxy resin and the (B2) maleimide structure in one molecule in the total solid content of the photosensitive resin composition excluding the (D) silica. It is preferable to contain 1 to 50% by mass of the maleimide compounds having the same.
  • the cured product of the present invention is characterized by being obtained by curing the photosensitive resin composition or the resin layer of the dry film.
  • a cured product having excellent reliability such as heat resistance and crack resistance
  • a photosensitive resin composition having excellent light characteristics (resolution) can be obtained from the composition.
  • a dry film having a resin layer, the composition or a cured product of the resin layer of the dry film, and an electronic component having the cured product can be provided.
  • the average coefficient of linear thermal expansion H is preferably 40 to 100 ppm / ° C.
  • the glass transition point (Tg) of the cured product obtained under the above-mentioned production conditions is preferably 170 ° C. or higher, more preferably 180 ° C. or higher.
  • the photosensitive resin composition of the present invention is a curable copolymer resin having (A) at least a first repeating unit represented by the following formula (1) and a second repeating unit represented by the following formula (2). Contains.
  • R 0 is a monovalent organic group having 1 to 30 carbon atoms
  • R 1 is a hydrogen atom or an organic group having 1 to 7 carbon atoms
  • R Reference numeral 2 is a single bond or an alkylene group having 1 to 5 carbon atoms
  • R 3 is a monovalent group having a thermocrosslinkability.
  • the monovalent organic group is a monovalent group having a carbon atom. Means the basis of.
  • the monovalent organic group having 1 to 30 carbon atoms that R 0 can take is an alkyl group having 1 to 30 carbon atoms such as a methyl group, an ethyl group, an isopropyl group and a lauryl group; a phenyl group.
  • aryl halide group having 1 to 30 carbon atoms such as a group; an alkoxysilylalkyl group having 1 to 30 carbon atoms such as an N- [3- (triethoxysilyl) propyl] group; and 1 carbon number such as a dodecenyl group and an octadecenyl group.
  • the monovalent organic group having 1 to 30 carbon atoms that can be taken by R 0 can have 20 or less carbon atoms, 15 or less carbon atoms, 10 or less carbon atoms, or 7 or less carbon atoms.
  • R 0 is preferably an organic group having 1 to 30 carbon atoms, an alkyl group having 1 to 30 carbon atoms, a phenyl group, an alkylaryl group having 7 to 30 carbon atoms, and 3 carbon atoms. It is preferably a cycloalkyl group of about 30 or an aralkyl group having 7 to 30 carbon atoms.
  • R 1 is preferably a hydrogen atom, an alkyl group having 1 to 7 carbon atoms, a phenyl group, an alkenyl group having 1 to 7 carbon atoms, or a carboxyl group, and is preferably a hydrogen atom or a carboxyl group. It is more preferably an alkyl group having 1 to 5 carbon atoms.
  • the alkylene group having 1 to 5 carbon atoms that can be taken by R 2 may have a substituent.
  • the alkylene group having 1 to 5 carbon atoms include a methylene group, an ethylene group, an n-propylene group, a trimethylene group and a butylene group.
  • the substituent include a hydroxyl group and the like.
  • the curable copolymer resin (A) requires a structural unit derived from the maleimide-based monomer represented by the formula (1) and a structural unit derived from the unsaturated carboxylic acid ester monomer represented by the formula (2) as essential units. It has as.
  • the curable copolymer resin (A) may have a structural unit derived from an unsaturated carboxylic acid monomer or the like, if necessary, and may contain a monomer having a functional group capable of reacting with a carboxyl group. It may have a structure formed by reacting.
  • the first repeating unit represented by the formula (1) is a maleimide-based monomer, that is, a repeating unit derived from a maleimide or a maleimide derivative.
  • maleimide or maleimide derivative examples include N-phenylmaleimide, N- (2-methylphenyl) maleimide, N- (4-methylphenyl) maleimide, and N- (2).
  • 6-diethylphenyl) maleimide N- (2-chlorophenyl) maleimide, N-methylmaleimide, N-ethylmaleimide, N-isopropylmaleimide, N-laurylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-phenyl Methylmaleimide, N- (2,4,6-tribromophenyl) maleimide, N- [3- (triethoxysilyl) propyl] maleimide, N-octadecenylmaleimide, N-dodecenylmaleimide, N- N-substituted maleimides such as (2-methoxyphenyl) maleimide, N- (2,4,6-trichlorophenyl) maleimide, N- (4-hydroxyphenyl) maleimide, N- (1-hydroxyphenyl) maleimide, and unsubstituted.
  • Maleimide can be mentioned, and one or a combination of two or more of these can be used.
  • N-phenylmaleimide, N- (2-methylphenyl) maleimide, and N- (2,6-diethylphenyl) have a large effect of improving heat resistance, good copolymerizability, and are easily available.
  • Maleimide, N-lauryl maleimide, N-cyclohexylmaleimide, N-benzylmaleimide and the like are preferable, N-phenylmaleimide, N-cyclohexylmaleimide and N-benzylmaleimide are more preferable, and N-phenylmaleimide and N-benzylmaleimide are most preferable. ..
  • N-phenylmaleimide and N-benzylmaleimide are also preferable to use.
  • the preferable ratio of N-phenylmaleimide and N-benzylmaleimide when used in combination is 99: 1 to 1:99 by mass ratio.
  • the maleimide-based monomer comprises all the monomer components (constituting the base polymer) constituting the polymer (base polymer) in (A) 100% by mass of the curable copolymer resin. It is preferably 10 to 60% by mass based on 100% by mass of all the monomer units.
  • the curable copolymer resin (A) preferably has 10 to 60% by mass of a constituent unit derived from the maleimide-based monomer represented by the formula (1) in 100% by mass of the main chain and an unsaturated carboxylic acid represented by the formula (2).
  • It may contain 10 to 40% by mass of a structural unit derived from an acid ester monomer, and may contain 10 to 40% by mass of a structural unit derived from an unsaturated carboxylic acid monomer, if necessary, and a radically polymerizable carbon-carbon in the side chain. It may have a double bond (ethylenically unsaturated group).
  • the maleimide-based monomer unit means a structural unit derived from the maleimide-based monomer when the maleimide-based monomer is copolymerized or graft-polymerized.
  • the (A) curable copolymer resin of the present invention may have at least a thermosetting reaction with the (B1) epoxy resin, but the components (A) may have ethylenically unsaturated groups capable of photocuring with each other. preferable.
  • the unsaturated carboxylic acid ester monomer will be described. Since the unsaturated carboxylic acid ester monomer has a thermally crosslinkable group such as a hydroxyl group, it reacts with the (B1) epoxy resin to improve the cured product properties.
  • the unsaturated carboxylic acid ester monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl (meth) acrylate.
  • hydroxyalkyl (meth) acrylates such as 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2,3-dihydroxypropyl (meth) acrylate, and 2-hydroxymethyl ( Meta) acrylamide, 2-hydroxyethyl (meth) acrylamide, 2-hydroxypropyl (meth) acrylamide, 3-hydroxypropyl (meth) acrylamide, 4-hydroxybutyl (meth) acrylamide, hydroxypivalyl (meth) acrylamide, 5- Examples thereof include (meth) acrylicoyl-based monomers such as hydroxyalkyl (meth) acrylamide such as hydroxypentyl (meth) acrylamide and 6-hydroxyhexyl (meth) acrylamide, and one or more of these can be used.
  • the unsaturated carboxylic acid ester monomer may be one in which the hydroxyl group (hydroxy group) of the above-exemplified monomer is changed to at least one of a carboxyl group, an amino group and a thiol group. That is, carboxyalkyl (meth) acrylate, aminoalkyl (meth) acrylate, and thioalkyl (meth) acrylate may be used.
  • Examples of other acid groups include functional groups that neutralize with alkaline water, such as phenolic hydroxyl groups, carboxylic acid anhydride groups, phosphoric acid groups, and sulfonic acid groups, and have only one of these groups. However, it may have two or more kinds.
  • the description for the carboxyl group also applies to the other acid groups described above.
  • copolymerizable monomer components may be used in obtaining the polymer (base polymer) as long as the properties are not adversely affected.
  • Specific examples of such monomer components include aromatic monomers; vinyl ester monomers such as vinyl acetate and vinyl adipate; methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate and the like.
  • Ether an acid anhydride group-containing monomer such as maleic anhydride, a monomer obtained by ring-opening the acid anhydride group with alcohols, or an unsaturated basic acid other than those described above; N-vinylpyrrolidone, Examples thereof include N-vinyl-based monomers such as N-vinyloxazolidone; cyano group-containing monomers such as acrylonitrile and methacrylonitrile.
  • aromatic monomers are preferable because they have good copolymerizability with maleimide-based monomers and also have excellent properties of cured products.
  • aromatic monomers include styrene, ⁇ -methylstyrene, ⁇ -chlorostyrene, vinyltoluene and the like, and styrene is most preferable because it has excellent electrical characteristics and is inexpensive.
  • a monomer having a sex unsaturated group is reacted to impart radical polymerizable property to obtain a radically polymerizable polymer.
  • the functional group capable of reacting with an acid group such as a carboxyl group is preferably selected from the group consisting of a glycidyl group, an oxazolinyl group, an isocyanate group and an oxetanyl group.
  • the radically polymerizable carbon-carbon double bond is preferably a (meth) acryloyl group.
  • a (meth) acryloyl group As specific monomers, glycidyl (meth) acrylate and 3,4-epoxycyclohexylmethyl (meth) acrylate are preferable.
  • the double bond equivalent is 600 to 4000 g / eq. It is preferable to carry out a radically polymerizable carbon-carbon double bond introduction reaction so as to be.
  • the double bond equivalent is related to the photocurability and the physical properties of the cured product, and by setting the double bond equivalent within the above range, a cured product having excellent physical properties such as heat resistance, strength and flexibility can be provided. In addition, a well-balanced photosensitive resin having both photocurability and alkali developability can be obtained.
  • a more preferred range of double bond equivalents is 700-3000 g / eq. And more preferably 800-2500 g / eq. Is.
  • the curable copolymer resin (A) has a carboxyl group
  • its acid value is preferably 30 mgKOH / g or more, more preferably 40 mgKOH / g or more, further preferably 50 mgKOH / g or more, and preferably 160 mgKOH / g or less. , 155 mgKOH / g or less is more preferable, and 150 mgKOH / g or less is further preferable.
  • the acid value of the curable copolymer resin (A) is 30 mgKOH / g or more, good alkali developability can be easily exhibited.
  • the acid value of the curable copolymer resin is 160 mgKOH / g or less, the exposed portion is less likely to be eroded by the alkaline developer, and the water resistance and moisture resistance of the cured product are improved.
  • the preferable range of the weight average molecular weight Mw of the curable copolymer resin (A) is determined by gel permeation chromatography (hereinafter, also referred to as “GPC”) in consideration of alkali developability, physical properties of the cured coating film, heat resistance and the like.
  • the measured value is preferably 1,000 to 100,000 in terms of polystyrene. Further, considering that the physical properties such as sensitivity and crack resistance are both better, it is more preferable that the weight average molecular weight of the (A) curable copolymer resin is less than 10,000.
  • the blending amount of the (A) curable copolymer resin is, for example, 10 to 80% by mass in the total solid content of the photosensitive resin composition of the present invention excluding (D) silica.
  • the photosensitive resin composition of the present invention may further contain an alkali-soluble resin different from the component (A).
  • the alkali-soluble resin may be any resin having an alkali-soluble group, and the alkali-soluble group is, for example, any one of a phenolic hydroxyl group, a thiol group and a carboxyl group.
  • the alkali-soluble resin include compounds having two or more phenolic hydroxyl groups, carboxyl group-containing resins, compounds having phenolic hydroxyl groups and carboxyl groups, and compounds having two or more thiol groups, and among them, excellent developability. Therefore, a carboxyl group-containing resin is preferable.
  • the carboxyl group-containing resin does not have to have an ethylenically unsaturated group, but a carboxyl group-containing photosensitive resin having an ethylenically unsaturated group is preferable from the viewpoint of photocurability and development resistance. ..
  • a (meth) acryloyl group is preferable.
  • the term (meth) acryloyl group is a general term for acryloyl groups, methacryloyl groups, and mixtures thereof, and the same applies to other similar expressions.
  • the alkali-soluble resin may be used alone or in combination of two or more.
  • Diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates and aromatic diisocyanates, carboxyl group-containing dialcoic compounds such as dimethylolpropionic acid and dimethylolbutanoic acid, polycarbonate-based polyols and polyether-based compounds.
  • 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, and a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group.
  • one isocyanate group and one or more (meth) acryloyl groups are formed in the molecule, such as an isophorone diisocyanate and a pentaerythritol triacrylate isomorphic reaction product.
  • a carboxyl group-containing photosensitive resin obtained by reacting a bifunctional or higher polyfunctional (solid) epoxy resin with (meth) acrylic acid and adding a dibasic acid anhydride to a hydroxyl group existing in a side chain.
  • Carboxylic acid obtained by reacting (meth) acrylic acid with a polyfunctional epoxy resin obtained by further epoxidizing the hydroxyl groups of a bifunctional (solid) epoxy resin with epichlorohydrin, and adding a dibasic acid anhydride to the generated hydroxyl groups.
  • Group-containing photosensitive resin obtained by reacting (meth) acrylic acid with a polyfunctional epoxy resin obtained by further epoxidizing the hydroxyl groups of a bifunctional (solid) epoxy resin with epichlorohydrin, and adding a dibasic acid anhydride to the generated hydroxyl groups.
  • Group-containing photosensitive resin Group-containing photosensitive resin.
  • a dicarboxylic acid such as adipic acid, phthalic acid, or hexahydrophthalic acid is reacted with a bifunctional oxetane resin, and the generated primary hydroxyl group is subjected to two bases such as phthalic anhydride, tetrahydrophthalic anhydride, and hexahydrophthalic 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).
  • an unsaturated group-containing monocarboxylic acid such as acrylic acid, maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, adipine with respect to the alcoholic hydroxyl group of the obtained reaction product.
  • a carboxyl group-containing resin obtained by reacting a polybasic anhydride such as an acid.
  • reaction production obtained by reacting a reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with alkylene oxide such as ethylene oxide and propylene oxide with an unsaturated group-containing monocarboxylic acid.
  • alkylene oxide such as ethylene oxide and propylene oxide
  • a carboxyl group-containing photosensitive resin obtained by reacting a substance with a polybasic acid anhydride.
  • a carboxyl group-containing photosensitive resin obtained by further adding a compound having one epoxy group and one or more (meth) acryloyl groups in one molecule to the resins (1) to (11).
  • the blending amount of the alkali-soluble resin is, for example, 0 to 70% by mass in the total solid content of the photosensitive resin composition of the present invention excluding (D) silica.
  • the photosensitive resin composition of the present invention contains (B1) epoxy resin.
  • the (B1) epoxy resin is preferably a compound having at least two or more epoxy groups in the molecule, that is, a polyfunctional epoxy compound.
  • epoxy resins may be used alone or in combination of two or more.
  • a novolak type epoxy resin a modified novolak type epoxy resin, a heterocyclic epoxy resin, a bixylenol type epoxy resin, or a mixture thereof is particularly preferable.
  • the blending amount of the (B1) epoxy resin is preferably 20 to 90% by mass based on the total solid content of the photosensitive resin composition of the present invention excluding (D) silica.
  • the photosensitive resin composition of the present invention contains a maleimide compound having (B2) two or more maleimide structures in one molecule.
  • the maleimide compound (B2) is not particularly limited, and a known and commonly used compound may be used.
  • examples of the (B2) maleimide compound include polyfunctional aliphatic or alicyclic maleimides and polyfunctional aromatic maleimides.
  • a polyfunctional aromatic maleimide is preferable, and a maleimide compound represented by the following general formula (I) is particularly preferable.
  • bismaleimide compounds have poor light transmittance, and when used in a photosensitive resin composition, resolution and sensitivity are lowered.
  • the heat resistance can be improved without impairing the optical characteristics such as resolution and sensitivity. It has become possible.
  • Examples of the maleimide compound represented by the following general formula (I) include MIR-3000 and MIR-3000-70T manufactured by Nippon Kayaku Co., Ltd.
  • R 4 may be the same or different, and represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group, or the like, and n is an integer of 1 ⁇ n ⁇ 5. Represents.
  • polyfunctional aliphatic or alicyclic maleimide examples include N, N'-methylenebismaleimide, N, N'-ethylenebismaleimide, tris (hydroxyethyl) isocyanurate and aliphatic / alicyclic maleimidecarboxylic acid.
  • Isocyanulate skeleton such as a maleimide ester compound having an isocyanurate skeleton obtained by dehydration esterification of and tris (carbamatehexyl) isocyanurate and a maleimide urethane compound having an isocyanurate skeleton obtained by urethaneizing an aliphatic / alicyclic maleimide alcohol.
  • n is an integer of 1 to 6
  • R 5 is a hydrogen atom or a methyl group.
  • oxime ester-based photopolymerization initiator examples include commercially available products such as IrgacureOXE01 and IrgacureOXE02 manufactured by BASF Japan, N-1919 and NCI-831 manufactured by ADEKA.
  • acylphosphine oxide-based photopolymerization initiator examples include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and bis (2,6).
  • -Dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide and the like are mentioned, and as commercially available products, Omnirad TPO manufactured by IGM Resins, Omnirad 819 manufactured by IGM Resins and the like are used. be able to.
  • titanosen-based photopolymerization initiator examples include bis (cyclopentadienyl) -di-phenyl-titanium, bis (cyclopentadienyl) -di-chloro-titanium, and bis (cyclopentadienyl).
  • -Bis (2,3,4,5,6 pentafluorophenyl) titanium, bis (cyclopentadienyl) -bis (2,6-difluoro-3- (pyrrole-1-yl) phenyl) titanium and the like can be mentioned.
  • Examples of commercially available products include Omnirad 784 manufactured by IGM Resins.
  • the photopolymerization initiator may be used alone or in combination of two or more.
  • the blending amount of the photopolymerization initiator (C) is preferably 0.005 to 40% by mass based on the total solid content of the photosensitive resin composition of the present invention excluding (D) silica.
  • the amount of the photopolymerization initiator is 0.005% by mass or more, the light irradiation time may be short and polymerization is likely to occur, so that an appropriate surface hardness can be obtained. Even if the photopolymerization initiator is blended in an amount of more than 40% by mass, there is little merit in using a large amount.
  • the silica is subjected to a surface treatment capable of introducing a curable reactive group.
  • a curable reactive group may be a group that undergoes a curing reaction with a component (for example, (A) curable copolymer resin, (B1) epoxy resin, or (B2) maleimide compound) to be blended in the photosensitive resin composition.
  • the present invention is not particularly limited, and may be a photocurable reactive group or a thermosetting reactive group.
  • thermosetting reactive group an amino group is more preferable.
  • the method for introducing a curable reactive group onto the surface of the coated silica particles is not particularly limited, and the curable reactive group may be introduced using a known and commonly used method, and a surface treatment agent having a curable reactive group, for example, a curable reaction
  • the surface of the coated silica particles may be treated with a coupling agent or the like having a group as an organic group.
  • a coupling agent a silane coupling agent, a titanium coupling agent, a zirconium coupling agent, an aluminum coupling agent and the like can be used. Of these, a silane coupling agent is preferable.
  • a liquid, solid or semi-solid photosensitive (meth) acrylate compound having one or more (meth) acryloyl groups in the molecule can be used at room temperature.
  • the photosensitive (meth) acrylate compound which is liquid at room temperature, has the purpose of increasing the photoreactivity of the composition, adjusting the composition to a viscosity suitable for various coating methods, and assisting in the solubility in an alkaline aqueous solution. Also fulfills.
  • the photosensitive resin composition of the present invention can contain a curing accelerator.
  • the curing accelerator include imidazole, 2-methylimidazole, 2-ethyl imidazole, 2-ethyl-4-methyl imidazole, 2-phenyl imidazole, 4-phenyl imidazole, 1-cyanoethyl-2-phenyl imidazole, 1-.
  • amine compounds are preferable because they improve dispersibility and fluidity.
  • a compound that also functions as an adhesion imparting agent is used in combination with a thermosetting catalyst.
  • the curing accelerator may be used alone or in combination of two or more.
  • the blending amount of the curing accelerator is, for example, 0.01 to 30% by mass in the total solid content of the composition.
  • the photosensitive resin composition of the present invention preferably contains an elastomer. Since the elastic modulus can be lowered by containing the elastomer, the stress at the time of curing can be relaxed and the crack resistance can be further improved.
  • known elastomers can be used, for example, polyester-based elastomers, styrene-based elastomers, polyurethane-based elastomers, polyester-urethane-based elastomers, polyamide-based elastomers, polyesteramide-based elastomers, acrylic-based elastomers, olefin-based elastomers, and silicones.
  • a system elastomer or the like can be used. Further, a resin obtained by modifying a part or all of the epoxy groups of an epoxy resin having various skeletons with both-terminal carboxylic acid-modified butadiene-acrylonitrile rubber can also be used. Further, epoxy-containing polybutadiene-based elastomers, acrylic-containing polybutadiene-based elastomers, hydroxyl group-containing polybutadiene-based elastomers, hydroxyl group-containing isoprene-based elastomers, block copolymers and the like can also be used.
  • the product names are R-45HT, Poly bd HTP-9 (manufactured by Idemitsu Kosan Co., Ltd.), Epolide PB3600 (manufactured by Daicel Chemical Co., Ltd.), Denarex R-45EPT (manufactured by Nagase ChemteX), Tough Serene (Sumitomo Chemical Co., Ltd.) , Ricon series (manufactured by Clay Valley), Hytrel (manufactured by Toray DuPont), Perprene (manufactured by Toyobo), Esper 1612, 1620 (manufactured by Hitachi Chemical Co., Ltd.) and the like. These elastomers can be used alone or in combination of two or more.
  • the blending amount of the elastomer is preferably 0.5 to 10% by mass based on the total solid content of the composition.
  • the photosensitive resin composition of the present invention may contain a colorant.
  • a colorant known colorants such as red, blue, green, yellow, black, and white can be used, and any of pigments, dyes, and pigments may be used. However, it is preferable that it does not contain halogen from the viewpoint of reducing the environmental load and affecting the human body.
  • the colorant one type may be used alone or two or more types may be used in combination.
  • the blending amount of the colorant is, for example, 0.01 to 10% by mass based on the total solid content of the composition.
  • a known and commonly used organic solvent such as a solvent can be used. These organic solvents may be used alone or in combination of two or more.
  • the photosensitive resin composition of the present invention may contain other additives known and commonly used in the field of electronic materials.
  • Other additives include thermal polymerization inhibitors, UV absorbers, silane coupling agents, plasticizers, flame retardants, antistatic agents, anti-aging agents, antioxidants, antibacterial / antifungal agents, defoamers, leveling.
  • the photosensitive 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 dry film of the present invention has a resin layer obtained by applying and drying the photosensitive resin composition of the present invention on a carrier film.
  • the photosensitive resin composition of the present invention is diluted with the above organic solvent to adjust the viscosity to an appropriate level, and then a comma coater, a blade coater, a lip coater, a rod coater, and a squeeze coater. , Reverse coater, transfer coater, gravure coater, spray coater, etc., and apply to a uniform thickness on the carrier film.
  • the applied composition is usually dried at a temperature of 40 to 130 ° C. for 1 to 30 minutes to form a resin layer.
  • the coating film thickness is not particularly limited, but is generally selected as appropriate in the range of 3 to 150 ⁇ m, preferably 5 to 60 ⁇ m after drying.
  • a plastic film is used, and for example, a polyester film such as polyethylene terephthalate (PET), a polyimide film, a polyamideimide film, a polypropylene film, a polystyrene film, or the like can be used.
  • PET polyethylene terephthalate
  • the thickness of the carrier film is not particularly limited, but is generally selected as appropriate in the range of 10 to 150 ⁇ m. More preferably, it is in the range of 15 to 130 ⁇ m.
  • the photosensitive resin composition of the present invention may be applied onto the cover film and dried to form a resin layer, and a carrier film may be laminated on the surface thereof. That is, either a carrier film or a cover film may be used as the film to which the photosensitive resin composition of the present invention is applied when the dry film is produced in the present invention.
  • the photosensitive resin composition of the present invention is suitably used for forming a cured film on an electronic component, particularly for forming a cured film on a printed wiring board, and more preferably for forming a permanent film. And more preferably used to form solder resists, interlayer insulating layers, and coverlays. Further, it is suitable for forming a permanent coating (particularly solder resist) for a printed wiring board, for example, a package substrate, particularly FC-BGA, which requires a high degree of reliability. Further, it can be suitably used for forming a permanent coating such as a solder resist of a printed wiring board exposed to a high temperature state for in-vehicle use.
  • the dropping was carried out from the dropping tanks 1, 2, 4 to 3 hours and from the dropping tank 3 for 2.5 hours. After the completion of the dropping, the reaction was continued at 80 ° C. for 30 minutes. Then, the reaction temperature was raised to 95 ° C., and the reaction was continued for 1.5 hours to obtain a polymer solution before the radical polymerizable double bond introduction reaction. Next, 9.9 parts of glycidyl methacrylate, 7.4 parts of carbitol acetate as a reaction catalyst, 0.7 parts of triphenylphosphine as a reaction catalyst, and Antage W-400 (manufactured by Kawaguchi Chemical Industry Co., Ltd.) as a polymerization inhibitor in this polymer solution.
  • [Preparation of filler] Preparation of methacrylic silane treated silica
  • 48 g of PMA as a solvent 48 g
  • 1 g of a silane coupling agent having a methacrylic group KBM-503 manufactured by Shin-Etsu Chemical Co., Ltd.
  • Examples 1 to 11, Comparative Examples 1 to 5 The various components shown in Tables 1 to 3 below are blended in the proportions (parts by mass) shown in Tables 1 to 3, diluted with an organic solvent to a viscosity that can be dispersed with a bead mill, premixed with a stirrer, and then bead milled.
  • the photosensitive resin composition was dispersed.
  • the obtained dispersion was passed through a filtration filter having an opening of 10 ⁇ m to obtain a photosensitive resin composition.
  • the ratio (parts by mass) in the table is the amount of solid content.
  • a dry film having a thickness of 10 to 15 ⁇ m prepared by the above method was heat-laminated on a CZ-treated copper-plated substrate using a vacuum laminator.
  • This substrate was exposed to a step tablet (Photo 41 step) using a projection exposure machine, and then a 1 wt% Na 2 CO 3 aqueous solution at 30 ° C. was developed under the condition of a spray pressure of 2 kg / cm 2 for 60 seconds.
  • This substrate was irradiated with ultraviolet rays in a UV conveyor furnace under the condition of an integrated exposure of 1000 mJ / cm 2 , and then heat-cured at 160 ° C. for 60 minutes.

Landscapes

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

Abstract

L'invention concerne une composition de résine photosensible ou similaire ayant d'excellentes propriétés optiques (résolution) et permettant d'obtenir un objet durci ayant une excellente fiabilité vis-à-vis de la résistance à la chaleur, de la résistance à la fissuration, etc. Cette composition de résine photosensible comprend (A) une résine de copolymère durcissable ayant au moins un premier motif récurrent représenté par la formule (1) et un second motif récurrent représenté par la formule (2), (B1) une résine époxy, (B2) un composé maléimide ayant au moins deux structures de maléimide dans une molécule, (C) un initiateur de photopolymérisation, et (D) de la silice, et elle est caractérisée en ce que la quantité de la silice (D) mélangée et convertie en ingrédients solides est de 25 à 75 % en masse, et lorsque la composition de résine photosensible est exposée à une lumière de 1 000 mJ/cm2 et chauffée à 160 °C pendant une heure pour obtenir un objet durci, la différence (H-L) entre le coefficient moyen de dilatation thermique linéaire (L) calculé dans la plage de 0 °C à 50 °C et le coefficient moyen de dilatation thermique linéaire (H) calculé dans la plage de 200 °C à 250 °C, pour cet objet durci, est supérieure à 20 ppm/°C mais inférieure ou égale à 60 ppm/°C.
PCT/JP2020/000762 2019-03-29 2020-01-10 Composition de résine photosensible, film sec, produit durci, et composant électronique WO2020202691A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2019069265A JP2020166214A (ja) 2019-03-29 2019-03-29 感光性樹脂組成物、ドライフィルム、硬化物、および、電子部品
JP2019-069265 2019-03-29

Publications (1)

Publication Number Publication Date
WO2020202691A1 true WO2020202691A1 (fr) 2020-10-08

Family

ID=72668082

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2020/000762 WO2020202691A1 (fr) 2019-03-29 2020-01-10 Composition de résine photosensible, film sec, produit durci, et composant électronique

Country Status (3)

Country Link
JP (1) JP2020166214A (fr)
TW (1) TW202102942A (fr)
WO (1) WO2020202691A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4063954A2 (fr) 2021-03-23 2022-09-28 Shin-Etsu Chemical Co., Ltd. Composition de résine photosensible positive, film sec photosensible positif, procédé de production de film sec photosensible positif, procédé de formation de motifs, procédé de formation d'un film durci, film d'isolation intercouche, film de protection de surface et composant électronique
WO2022211120A1 (fr) * 2021-03-31 2022-10-06 太陽インキ製造株式会社 Structure de résine durcissable stratifiée, film sec, produit durci et composant électronique

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07330874A (ja) * 1994-06-01 1995-12-19 Toshiba Corp 樹脂組成物および樹脂封止型半導体装置
JP2003020403A (ja) * 2001-07-10 2003-01-24 Nippon Kayaku Co Ltd 樹脂組成物、ソルダーレジスト樹脂組成物及びこれらの硬化物
JP2010128275A (ja) * 2008-11-28 2010-06-10 Hitachi Chem Co Ltd 感光性樹脂組成物、これを用いた感光性フィルム及び永久レジスト
JP2010160419A (ja) * 2009-01-09 2010-07-22 Hitachi Chem Co Ltd 感光性樹脂組成物、感光性フィルム、レジストパターンの形成方法及びそれを用いた永久レジスト。
JP2012073601A (ja) * 2010-08-31 2012-04-12 Fujifilm Corp 感光性組成物、並びに、感光性フィルム、永久パターン、永久パターン形成方法、及びプリント基板
WO2013172434A1 (fr) * 2012-05-17 2013-11-21 太陽インキ製造株式会社 Composition de maléimide développable en milieu liquide et carte de circuit imprimé
WO2014125884A1 (fr) * 2013-02-12 2014-08-21 東レ株式会社 Composition de résine photosensible, film protecteur ou film isolant obtenu par thermodurcissement de ladite composition, écran tactile utilisant ledit film et procédé de production pour ledit écran tactile
JP2015067699A (ja) * 2013-09-27 2015-04-13 株式会社日本触媒 硬化性樹脂組成物及びその用途
WO2015141618A1 (fr) * 2014-03-17 2015-09-24 旭化成イーマテリアルズ株式会社 Composition de résine photosensible, procédé de production de motif en relief durci et dispositif semi-conducteur

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07330874A (ja) * 1994-06-01 1995-12-19 Toshiba Corp 樹脂組成物および樹脂封止型半導体装置
JP2003020403A (ja) * 2001-07-10 2003-01-24 Nippon Kayaku Co Ltd 樹脂組成物、ソルダーレジスト樹脂組成物及びこれらの硬化物
JP2010128275A (ja) * 2008-11-28 2010-06-10 Hitachi Chem Co Ltd 感光性樹脂組成物、これを用いた感光性フィルム及び永久レジスト
JP2010160419A (ja) * 2009-01-09 2010-07-22 Hitachi Chem Co Ltd 感光性樹脂組成物、感光性フィルム、レジストパターンの形成方法及びそれを用いた永久レジスト。
JP2012073601A (ja) * 2010-08-31 2012-04-12 Fujifilm Corp 感光性組成物、並びに、感光性フィルム、永久パターン、永久パターン形成方法、及びプリント基板
WO2013172434A1 (fr) * 2012-05-17 2013-11-21 太陽インキ製造株式会社 Composition de maléimide développable en milieu liquide et carte de circuit imprimé
WO2014125884A1 (fr) * 2013-02-12 2014-08-21 東レ株式会社 Composition de résine photosensible, film protecteur ou film isolant obtenu par thermodurcissement de ladite composition, écran tactile utilisant ledit film et procédé de production pour ledit écran tactile
JP2015067699A (ja) * 2013-09-27 2015-04-13 株式会社日本触媒 硬化性樹脂組成物及びその用途
WO2015141618A1 (fr) * 2014-03-17 2015-09-24 旭化成イーマテリアルズ株式会社 Composition de résine photosensible, procédé de production de motif en relief durci et dispositif semi-conducteur

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4063954A2 (fr) 2021-03-23 2022-09-28 Shin-Etsu Chemical Co., Ltd. Composition de résine photosensible positive, film sec photosensible positif, procédé de production de film sec photosensible positif, procédé de formation de motifs, procédé de formation d'un film durci, film d'isolation intercouche, film de protection de surface et composant électronique
WO2022211120A1 (fr) * 2021-03-31 2022-10-06 太陽インキ製造株式会社 Structure de résine durcissable stratifiée, film sec, produit durci et composant électronique

Also Published As

Publication number Publication date
JP2020166214A (ja) 2020-10-08
TW202102942A (zh) 2021-01-16

Similar Documents

Publication Publication Date Title
KR102135506B1 (ko) 감광성 드라이 필름 및 그것을 사용한 프린트 배선판의 제조 방법
KR101604557B1 (ko) 광경화성 열경화성 수지 조성물
JP6258547B2 (ja) 感光性ドライフィルムおよびそれを用いたプリント配線板の製造方法
WO2010117056A1 (fr) Résine photodurcissable et composition de résine photodurcissable
JP2010224168A (ja) 光硬化性熱硬化性樹脂組成物、そのドライフィルム及び硬化物並びにそれらを用いたプリント配線板
JP2009086414A (ja) 感光性樹脂組成物及びその硬化物
JP6877202B2 (ja) ネガ型光硬化性樹脂組成物、ドライフィルム、硬化物およびプリント配線板
KR20100051563A (ko) 난연성 광경화성 수지 조성물, 그의 드라이 필름 및 경화물, 및 이들을 이용한 인쇄 배선판
JP5355845B2 (ja) 光硬化性樹脂組成物、及びその硬化物。
JP2020148815A (ja) 硬化性樹脂組成物、そのドライフィルムおよび硬化物、これを有する電子部品並びに硬化性樹脂組成物の硬化物の製造方法
JP5338009B2 (ja) 光硬化性熱硬化性樹脂組成物及びその硬化物並びにそれらを用いたプリント配線板
WO2020202691A1 (fr) Composition de résine photosensible, film sec, produit durci, et composant électronique
JP5660690B2 (ja) 感光性樹脂組成物及びその硬化物
JP7216480B2 (ja) 光硬化性熱硬化性樹脂組成物及びドライフィルム及び硬化物ならびにプリント配線板
WO2020202690A1 (fr) Composition de résine durcissable, film sec, produit durci et composant électronique
JP6783600B2 (ja) 硬化性樹脂組成物、ドライフィルム、プリント配線板、および、プリント配線板の製造方法
TWI770369B (zh) 鹼顯像型感光性樹脂組成物、乾膜、硬化物，及印刷配線板
TWI696041B (zh) 感光性薄膜層合體及使用其所形成之硬化物
TW202136404A (zh) 硬化性樹脂組成物、乾膜、硬化物及電子零件

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 20784277

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 20784277

Country of ref document: EP

Kind code of ref document: A1