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WO2020108420A1 - Photo-initiateur hybride à base d'hexaarylbiimidazole - Google Patents

Photo-initiateur hybride à base d'hexaarylbiimidazole Download PDF

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WO2020108420A1
WO2020108420A1 PCT/CN2019/120523 CN2019120523W WO2020108420A1 WO 2020108420 A1 WO2020108420 A1 WO 2020108420A1 CN 2019120523 W CN2019120523 W CN 2019120523W WO 2020108420 A1 WO2020108420 A1 WO 2020108420A1
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meth
photosensitive resin
acrylate
bis
resin composition
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Chinese (zh)
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钱彬
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Chan N Changzhou Green Photosensitive Materials Co Ltd
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Chan N Changzhou Green Photosensitive Materials Co Ltd
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Application filed by Chan N Changzhou Green Photosensitive Materials Co Ltd filed Critical Chan N Changzhou Green Photosensitive Materials Co Ltd
Priority to KR1020217020297A priority Critical patent/KR102542061B1/ko
Priority to JP2021530322A priority patent/JP7680744B2/ja
Priority to MYPI2021002957A priority patent/MY204061A/en
Publication of WO2020108420A1 publication Critical patent/WO2020108420A1/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
    • 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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
    • C08F220/343—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate in the form of urethane links
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
    • 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
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • 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
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers

Definitions

  • the invention belongs to the field of organic chemistry, and in particular relates to a 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyldiimidazole mixed photoinitiator and a photosensitive containing the same Resin composition and its application.
  • photosensitive resin compositions with high sensitivity, high resolution, and resolution have become a hot spot for research.
  • the photoinitiator is required to have high initiation efficiency, good compatibility with the system, good solubility and other excellent properties.
  • the free radical polymerization system due to the special chemical structure of the hexaarylbisimidazole compounds, it can be photolyzed to produce macromolecular radicals under the action of ultraviolet light, thus becoming a very important photoinitiator in the photosensitive resin composition Agent.
  • BCIM 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyldiimidazole
  • the object of the present invention is to provide a BCIM mixed photoinitiator containing isomers with specific connection sites. Compared with the existing BCIM products, the photoinitiator of the invention has stable and excellent application performance, and has obvious advantages in sensitivity and the like.
  • the 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyldiimidazole mixed photoinitiator of the present invention mainly contains a 1-2' connection site
  • the compound of formula (I) and the compound of formula (II) having a 2′-3 linking position, and the sum of the contents of the two compounds accounts for more than 97% of the mixed photoinitiator,
  • Another object of the present invention is to provide a photosensitive resin composition
  • a photosensitive resin composition comprising the above 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyldiimidazole mixed photoinitiator and the Application of the composition in the field of light curing.
  • the 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyldiimidazole mixed photoinitiator of the present invention is applied to a photosensitive resin composition with excellent sensitivity and good resolution It can be widely used in the manufacture of printed circuit boards, protective patterns, conductor patterns, lead wires, semiconductor packages, etc. through dry and wet films.
  • the 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyldiimidazole mixed photoinitiator of the present invention contains a compound of formula (I) with a 1-2' attachment position And a compound of formula (II) having a 2'-3 connection position, and the sum of the two compounds accounts for more than 97% of the mixed photoinitiator,
  • the compound of formula (I) and the compound of formula (II) are not particularly limited, as long as the sum of the two contents meets the above requirements to achieve the object of the present invention.
  • 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyldiimidazole also has 1-4', 1-5', 3-4', 3-5', 1-1', 1-3', 3-3' and other linking isomers, but only meet the structure and content of the present invention
  • the required 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyldiimidazole mixed photoinitiator can show the optimal sensitivity.
  • the sum of the two contents is less than 97%, the sensitivity of BCIM tends to be significantly lower.
  • the content of the components in the BCIM mixed photoinitiator is detected by high performance liquid chromatography.
  • the synthesis method of 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyldiimidazole is a kind of photoinitiator known in the photoresist field, which can be substituted by triphenyl It is prepared by oxidative coupling of imidazole compounds.
  • the oxidizing agent used in the reaction can be exemplified by sodium hypochlorite, potassium ferricyanide, etc.
  • the phase transfer catalyst used can be exemplified by tetrabutylammonium bromide, benzyltriethylammonium chloride, crown Ether (15-crown-5, 18-crown-6), polyethylene glycol, etc.
  • composition of the invention requires 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyldiimidazole mixed photoinitiator.
  • the solvent may be one or a combination of two or more of toluene, pure benzene, methanol, ethanol, ethyl acetate, dichloromethane, and water.
  • the present invention also relates to a photosensitive resin composition containing the above 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyldiimidazole mixed photoinitiator.
  • the composition further includes: alkali soluble Polymers, compounds with ethylenically unsaturated double bonds, other photoinitiators and/or sensitizers, and optional auxiliaries.
  • the component 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyldiimidazole mixed photoinitiator is as shown above.
  • the content of 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyldiimidazole mixed photoinitiator is preferably 1- 10 parts by mass. Within this content range, the 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyldiimidazole mixed photoinitiator exhibits excellent photosensitizing activity and resolution while simultaneously With better system compatibility.
  • the alkali-soluble polymer can impart a film-forming function to the photosensitive resin composition.
  • As the alkali-soluble polymer as long as it has such characteristics, it can be applied without particular limitation.
  • the applicable alkali-soluble polymer may be (meth)acrylic polymer, styrene polymer, epoxy polymer, aliphatic polyurethane (meth)acrylate polymer, aromatic polyurethane (method Group) acrylate polymer, amide resin, amide epoxy resin, alkyd resin, phenol resin, etc.
  • the alkali-soluble polymer can be obtained by radical polymerization of a polymerizable monomer.
  • the polymerizable monomer include styrene, vinyl toluene, ⁇ -methylstyrene, p-methylstyrene, p-ethylstyrene, p-chlorostyrene, etc.
  • Maleic acid monoester fumaric acid, cinnamic acid, ⁇ -cyanocinnamic acid, itaconic acid, crotonic acid, propanoic acid, N-vinyl caprolactam; N-vinyl pyrrolidone, etc.
  • These polymerizable monomers may be used alone or in combination of two or more.
  • the alkali-soluble polymer having a carboxyl group may be an acrylic resin containing (meth)acrylic acid as a monomer unit, which is introduced into the carboxyl group by using (meth)acrylic acid as a monomer unit; it may further contain (meth)acrylic acid in addition ( A copolymer of alkyl methacrylate as a monomer unit; it may also contain a polymerizable monomer other than (meth)acrylic acid and alkyl (meth)acrylate in addition to (meth)acrylic acid (such as , A monomer having an ethylenically unsaturated group) as a monomer component copolymer.
  • the carboxyl group-containing alkali-soluble polymer can be obtained by radical polymerization of a polymerizable monomer having a carboxyl group and other polymerizable monomers, especially from (meth)acrylate, ethylenically unsaturated carboxylic acid and other (Meth) acrylate polymer made by copolymerization of comonomers.
  • the (meth)acrylate may be methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate , Hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, (meth)acrylic acid Decyl ester, undecyl (meth)acrylate, dodecyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, diethyl (meth)acrylate Aminoethyl, (meth)acrylate dimethylaminoethyl, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, furfuryl (meth)acrylate
  • the ethylenically unsaturated carboxylic acid is preferably at least one of acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, and particularly preferably acrylic acid and/or methacrylic acid.
  • the other copolymerizable monomers are preferably (meth)acrylamide, n-butyl (meth)acrylate, styrene, vinylnaphthalene, (meth)acrylonitrile, vinyl acetate, vinylcyclohexane At least one of them.
  • the alkali-soluble polymer may be used alone or in combination of two or more.
  • Examples of the alkali-soluble polymers used in combination of two or more include two or more types of alkali-soluble polymers composed of different copolymerization components, two or more types of alkali-soluble polymers with different weight average molecular weights, and two types with different degrees of dispersion. The above alkali-soluble polymers, etc.
  • the weight-average molecular weight of the alkali-soluble polymer is not particularly limited, but in terms of mechanical strength and alkali developability, the weight-average molecular weight is preferably 15,000 to 200,000, and more preferably 30,000 to 150,000, particularly preferably 30000-120000.
  • the weight average molecular weight is greater than 15,000, the developer resistance after exposure tends to be further improved, and when the weight average molecular weight is less than 200,000, the development time tends to become shorter, and can maintain other components such as photoinitiator Of compatibility.
  • the weight-average molecular weight of the alkali-soluble polymer is measured by gel permeation chromatography (GPC), and is obtained by conversion using a standard curve of standard polystyrene.
  • the acid value of the alkali-soluble polymer is preferably 50-300 mgKOH/g, more preferably 50-250 mgKOH/g, still more preferably 70-250 mgKOH/g, and particularly preferably 100- 250mgKOH/g.
  • the acid value of the alkali-soluble resin is less than 50 mgKOH/g, it is difficult to ensure a sufficient development speed.
  • it exceeds 300 mgKOH/g the adhesion is reduced, pattern short-circuiting is likely to occur, and the storage stability and viscosity of the composition are prone to occur. The problem of rising.
  • the molecular weight distribution [weight average molecular weight (Mw)/number average molecular weight (Mn)] of the alkali-soluble resin is preferably 1.5 to 6.0, and particularly preferably 1.8 to 3.7. When the molecular weight distribution is within the above range, the developability is excellent.
  • the content of the alkali-soluble polymer in the composition is preferably 20 to 70 parts by mass, more preferably 30 to 60 parts by mass based on 100 parts by mass of the total photosensitive resin composition.
  • the content of the alkali-soluble polymer is 20 parts by mass or more, the durability of the photosensitive resin composition to plating treatment, etching treatment, etc. can be improved, and when the content is 70 parts by mass or less, it is beneficial to improve the photosensitive resin composition Sensitivity.
  • the compound having an ethylenically unsaturated double bond can promote the film formation of the photosensitive resin composition.
  • the type of compound having an ethylenically unsaturated double bond is not particularly limited, as long as it is a photopolymerizable compound having at least one ethylenically unsaturated bond in the molecule.
  • Illustrative examples include: compounds obtained by reacting ⁇ , ⁇ -unsaturated carboxylic acids with polyols, bisphenol A (meth)acrylate compounds, ⁇ , ⁇ -unsaturated carboxylic acids and glycidol-containing Carboxylate monomers such as compounds obtained by reaction of compounds based on compounds, (meth)acrylate compounds having urethane bonds in the molecule, nonylphenoxyethyleneoxy (meth)acrylate, nonyl Phenoxy octaethyleneoxy (meth)acrylate, ⁇ -chloro- ⁇ -hydroxypropyl- ⁇ '-(meth)acryloyloxyethyl-phthalate, ⁇ -hydroxyl Ethyl- ⁇ '-(meth)acryloyloxyethyl
  • polyethylene glycol di(meth)acrylate having 2 to 14 ethyleneoxy groups and propylene oxide can be exemplified.
  • EO means ethylene oxide
  • PO means propylene oxide
  • PO-modified compound means having an oxypropylene group Block structure of the compound.
  • bisphenol A (meth)acrylate compound examples include 2,2-bis(4-((meth)acryloyloxypolyethoxy)phenyl)propane, 2 ,2-bis(4-((meth)acryloyloxypolypropoxy)phenyl)propane, 2,2-bis(4-((meth)acryloyloxypolybutoxy)phenyl ) Propane, 2,2-bis(4-((meth)acryloyloxypolyethoxypolypropoxy)phenyl)propane, etc.
  • 2,2-bis(4-((meth)acryloyloxypolyethoxy)phenyl)propane examples include: 2,2-bis(4-((methyl) Acryloyloxy diethoxy)phenyl)propane, 2,2-bis(4-((meth)acryloyloxytriethoxy)phenyl)propane, 2,2-bis(4-( (Meth)acryloyloxytetraethoxy)phenyl)propane, 2,2-bis(4-((meth)acryloyloxypentethoxy)phenyl)propane, 2,2-bis (4-((meth)acryloyloxyhexaethoxy)phenyl)propane, 2,2-bis(4-((meth)acryloyloxyheptethoxy)phenyl)propane, 2 ,2-bis(4-((meth)acryloyloxyoctaethoxy)phenyl)propane, 2,2-bis(4-((meth)
  • the number of oxyethylene groups in a single 2,2-bis(4-((meth)acryloyloxypolyethoxy)phenyl)propane molecule is preferably 4-20, more preferably 8-15. These compounds may be used alone or in combination of two or more.
  • Examples of the (meth)acrylate compound having a urethane bond in the molecule include (meth)acrylic monomers having an OH group at the ⁇ position and diisocyanate compounds (eg, isophor). Ketone diisocyanate, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate, 1,6-hexamethylene diisocyanate, etc.) addition reaction product, tri((meth)acryloyloxytetramethylene (Ethyl glycol isocyanate) hexamethylene isocyanurate, EO modified urethane di(meth)acrylate, PO modified urethane di(meth)acrylate, EO, PO modified urethane di (Meth)acrylate. These compounds may be used alone or in combination of two or more.
  • diisocyanate compounds eg, isophor
  • nonylphenoxy polyvinyloxy acrylate examples include nonylphenoxy tetravinyloxy acrylate, nonylphenoxy pentavinyloxy acrylate, nonylphenoxy Hexavinyloxy acrylate, nonylphenoxy heptaethyleneoxy acrylate, nonylphenoxy octaethyleneoxy acrylate, nonylphenoxy nonavinyloxy acrylate, nonylphenoxy deca Vinyloxy acrylate, nonylphenoxy undecyloxy acrylate. These compounds may be used alone or in combination of two or more.
  • phthalic acid compounds examples include ⁇ -chloro- ⁇ -hydroxypropyl- ⁇ '-(meth)acryloyloxyethyl phthalate and ⁇ -hydroxyalkane. - ⁇ '-(meth)acryloyloxyalkyl phthalate. These compounds may be used alone or in combination of two or more.
  • Examples of the aforementioned (meth)acrylic acid alkyl esters include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, and (meth)acrylic acid.
  • methyl (meth)acrylate preferred are methyl (meth)acrylate, ethyl (meth)acrylate, trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, Pentaerythritol tri(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexaacrylate. These compounds may be used alone or in combination of two or more.
  • the compound having an ethylenically unsaturated double bond is preferably selected from a bisphenol A (meth)acrylate compound and a compound having a urethane bond in the molecule (Meth) acrylate compounds. From the viewpoint of improving sensitivity and resolution, bisphenol A-based (meth)acrylate compounds are preferred.
  • 2,2-bis(4-((meth)acryloyloxypolyethoxy)phenyl)propane such as Shin Nakamura Chemical Industry Co., Ltd., BPE-200
  • polyethoxybisphenol A methacrylate such as Shin Nakamura Chemical Industry Co., Ltd., BPE-5000; Hitachi Chemical Co., Ltd., FA-321M
  • 2-bis(4-((meth)acryloyloxypolybutoxy)phenyl)propane such as Shin Nakamura Chemical Industry Co., Ltd., BPE-1300
  • the content of the compound having an ethylenically unsaturated double bond is preferably 20-50 parts by mass, and more preferably 25-45 parts by mass.
  • the sensitivity and resolution of the photosensitive resin composition will be further improved; when the content is less than 50 parts by mass, the photosensitive resin composition is easier It is thinned and the durability against etching is further improved.
  • the photosensitive resin composition also contains other photoinitiators or sensitizers to increase the compatibility, sensitivity, and resolution of the photosensitive resin system through a synergistic effect.
  • the other photoinitiators and/or sensitizers may include (but not limited to) bisimidazoles, pyrazolines, aromatic ketones, anthraquinones, benzoin and benzoin alkyl ethers, Oxime esters, triazines, triphenylamines, coumarins, thioxanthones, acridines and other photoinitiators known to those skilled in the art. These photoinitiators can be used alone or in combination of two or more.
  • the biimidazole derivative may be 2,2',5-tris(2-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenyl -Diimidazole, 2,2',5-tris(2-fluorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenyl-diimidazole, 2, 2'-bis(2,4-dichlorophenyl)-4,4'5,5'-tetraphenyl-diimidazole, 2,2'-bis(2-fluorophenyl)-4-(2- Chlorophenyl)-5-(3,4-dimethoxyphenyl)-4',5'-diphenyl-diimidazole, 2,2'-bis(2-fluorophenyl)-4,4 ',5,5'-tetraphenyl-diimidazole, 2,2'-bis(2-me
  • the pyrazoline compound may be 1-phenyl-3-(4-tert-butylstyryl)-5-(4-tert-butylphenyl)pyrazoline, 1-phenyl-3 -Biphenyl-5-(4-tert-butylphenyl) pyrazoline, ethoxylated (9) trimethylol pyrazoline ester, ethoxylated (10) bisphenol A pyrazoline ester And the like.
  • These pyrazoline compounds may be used alone or in combination of two or more.
  • the aromatic ketone derivative may be acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, benzophenone, 4-benzoyldiphenyl sulfide, 4-benzoyl-4'-methyldiphenyl sulfide, 4-benzoyl-4'- Ethyl diphenyl sulfide, 4-benzoyl-4'-propyl diphenyl sulfide, 4,4'-bis(diethylamino) benzophenone, 4-p-toluene mercaptobenzophenone, 2,4,6-trimethylbenzophenone, 4-methylbenzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(methyl, ethyl Base amino) benzophenone, acetophenone dimethyl ketal, benzyl dimethyl ketal, ⁇
  • the anthraquinone derivative may be 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 2,3-dimethylanthraquinone , 2-ethylanthracene-9,10-diethyl, 1,2,3-trimethylanthracene-9,10-dioctyl fat, 2-ethylanthracene-9,10-bis(4-chlorobutane Methyl ester), 2-(3-((3-ethyloxetan-3-yl)methoxy)-3-oxopropyl)anthracene-9,10-diethyl ester, 9, 10-Dibutoxyanthracene, 9,10-diethoxy-2-ethylanthracene, 9,10-bis(3-chloropropoxy)anthracene, 9,10-bis(2-hydroxyethy
  • benzoin and benzoin alkyl ether derivatives may be benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether, and the like. These benzoin and benzoin alkyl ether derivatives can be used alone or in combination of two or more.
  • the oxime ester derivative may be 1-(4-phenylthiophenyl)-n-octane-1,2-dione-2-benzoic acid oxime ester, 1-(6-(2-methyl Benzoyl)-9-ethylcarbazol-3-yl)-ethane-1-one-oxime acetate, 1-(6-(2-methylbenzoyl)-9-ethylcarbazole -3-yl)-butane-1-one-oxime acetate, 1-(6-(2-methylbenzoyl)-9-ethylcarbazol-3-yl)-propane-1-one- Oxime acetate, 1-(6-(2-methylbenzoyl)-9-ethylcarbazol-3-yl)-1-cyclohexyl-methane-1-one-oxime acetate, 1-(6 -(2-methylbenzoyl)-9-ethylcarbazol-3-yl)-3-cyclopenty
  • the triazine derivative may be 2-(4-ethylbiphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(3,4- Methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 3- ⁇ 4-[2,4-bis(trichloromethyl)-s-triazine -6-yl]phenylthio ⁇ propionic acid, 1,1,1,3,3,3-hexafluoroisopropyl-3- ⁇ 4-[2,4-bis(trichloromethyl)-s- Triazin-6-yl]phenylthio ⁇ propionate, ethyl-2- ⁇ 4-[2,4-bis(trichloromethyl)-s-triazin-6-yl]phenylthio ⁇ ethyl Ester, 2-ethoxyethyl-2- ⁇ 4-[2,4-bis(trichloromethyl)-s-triazin-6-yl
  • the triphenylamine compound may be N,N-bis-[4-(2-styryl-1-yl)-phenyl]-N,N-bis(2-ethyl-6methylbenzene Group)-1,1-bisphenyl-4,4-diamine, N,N-bis-[4-(2-styryl-1-yl)-4′-methylphenyl]-N, N-bis(2-ethyl-6methylphenyl)-1,1-bisphenyl-4,4-diamine and the like.
  • These triphenylamine compounds may be used alone or in combination of two or more.
  • the coumarin derivative may be 3,3'-carbonylbis(7-diethylamine coumarin), 3-benzoyl-7-diethylamine coumarin, 3,3'-carbonyl Bis(7-methoxycoumarin), 7-(diethylamino)-4-methylcoumarin, 3-(2-benzothiazole)-7-(diethylamino)coumarin , 7-(diethylamino)-4-methyl-2H-1-benzopyran-2-one (7-(diethylamino)-4-methylcoumarin), 3-benzoyl- 7-Methoxycoumarin, and the like.
  • These coumarin derivatives can be used alone or in combination of two or more.
  • the thioxanthone derivative may be thioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2-chlorothioxanthone, 1-chloro-4-propoxythioxanthone, isopropylthioxanthone, diisopropylthioxanthone, and the like.
  • These thioxanthone derivatives can be used alone or in combination of two or more.
  • the acridine derivatives may be 9-phenyl acridine, 9-p-methylphenyl acridine, 9-m-methylphenyl acridine, 9-o-chlorophenyl acridine, 9-o [4-(9-acridinyl)phenoxy]acetate of fluorophenylacridine, 2-ethyl-2-(hydroxymethyl)-1,3-propanediol ether cyclohexane ether, 1, 7-bis(9-acridinyl)heptane, 9-ethylacridine, 9-(4-bromophenyl)acridine, 9-(3-chlorophenyl)acridine, 1,7-bis( 9-acridine) heptane, 1,5-bis(9-acridinepentane), 1,3-bis(9-acridine)propane, and the like.
  • These acridine derivatives can
  • the content of the other photoinitiator or sensitizer is not more than 8 parts by mass.
  • the photosensitive resin composition of the present invention may optionally contain an appropriate amount of other auxiliary agents as needed.
  • the auxiliary agent may be dyes such as malachite green, tribromophenyl sulfone, colorless crystal violet and other light color developers, pigments, fillers, plasticizers, stabilizers, coating aids, peeling accelerators, etc. .
  • dyes, pigments, and photochromic agents exemplarily, tris(4-dimethylaminophenyl)methane, tris(4-dimethylamino-2methylphenyl)methane, fluorane Phthalocyanines such as dyes, toluenesulfonic acid monohydrate, basic magenta, phthalocyanine green and phthalocyanine blue, auramine, by-product magenta, crystal violet, methyl orange, Nile blue 2B, Victoria blue, peacock Green, Diamond Green, Basic Blue 20, Brilliant Green, Eosin, Ethyl Violet, Erythrosine Sodium B, Methyl Green, Phenolphthalein, Alizarin Red S, Thymol Phenolphthalein, Methyl Violet 2B, Quinadine Red, Rose Bengal Agar, Mitaniel Yellow, Thymol Sulfophthalein, Xylenol Blue, Methyl Orange, Orange IV, Diphenyl Fluorane Phthalocyanines
  • tris(4-dimethylaminophenyl)methane ie, leuco crystal violet, LCV.
  • These dyes, pigments and photochromic agents may be used alone or in combination of two or more.
  • fillers such as silica, alumina, talc, calcium carbonate, and barium sulfate (excluding the above-mentioned inorganic pigments) may be used.
  • the filler may be used alone or in combination of two or more.
  • plasticizer for example, it may be: phthalate such as dibutyl phthalate, diheptyl phthalate, dioctyl phthalate, diallyl phthalate, etc.
  • Glycol esters such as acid esters, triethylene glycol diacetate, tetraethylene glycol diacetate, sulfonamides such as p-toluenesulfonamide, benzenesulfonamide, n-butylbenzenesulfonamide, triphenyl phosphate, Trimethyl phosphate, triethyl phosphate, triphenyl phosphate, tricresyl phosphate, tricresyl phosphate, tolyl diphenyl phosphate, tricresyl phosphate, 2-naphthyl Diphenyl phosphate, tolyl bis 2,6-xylyl phosphate, aromatic condensed phosphate, tri(chloropropy
  • the above stabilizer exemplarily, it may be: hydroquinone, 1,4,4-trimethyl-diazobicyclo(3.2.2)-non-2-ene-2,3-dioxide, 1 -Phenyl-3-pyrazolidone, p-methoxyphenol, alkyl and aryl substituted hydroquinones and quinones, tert-butylcatechol, 1,2,3-pyrogallol, copper resinate, naphthalene Amine, ⁇ -naphthol, cuprous chloride, 2,6-di-tert-butyl-p-cresol, phenothiazine, pyridine, nitrobenzene, dinitrobenzene, p-toluoquinone and chloroquinone.
  • the stabilizer may be used alone or in combination of two or more.
  • the coating aid from the viewpoint of safety and versatility, it may be: acetone, methanol, methyl alcohol, ethyl alcohol, isopropyl alcohol, methyl ethyl ketone, propylene glycol monomethyl ether acetate , Ethyl lactate, cyclohexanone, ⁇ -butyrolactone, dichloromethane, etc.
  • the coating aid may be used alone or in combination of two or more.
  • peeling accelerator exemplarily, it may be: benzenesulfonic acid, toluenesulfonic acid, xylenesulfonic acid, phenolsulfonic acid, methyl, propyl, heptyl, octyl, decyl, dodecyl, etc. Alkylbenzenesulfonic acid etc.
  • the peeling accelerator may be used alone or in combination of two or more.
  • the content of the auxiliary agent is not more than 10 parts by mass.
  • the photosensitive resin composition of the present invention can be prepared as a dry film, that is, a photosensitive resin laminate, and is used in the manufacture of printed circuit boards, protective patterns, conductor patterns, lead wires, and semiconductor packages through different processes in different The desired pattern is formed on the substrate.
  • the photosensitive resin composition of the present invention can also be applied to the corresponding substrate in each corresponding manufacturing step by a wet film coating machine, that is, used as a wet film for printed circuit boards, protective patterns, conductor patterns, frame wires, In the manufacture of semiconductor packages, different patterns are formed on different substrates through different processes.
  • the photosensitive resin laminate which is a dry film of the present invention includes a photosensitive resin layer formed of a photosensitive resin composition and a support that supports the photosensitive resin layer.
  • the production of a dry film includes: coating a photosensitive resin composition on a support and drying to form a photosensitive resin layer; optionally, attaching a cover film (protective layer) as needed.
  • the drying condition is at 60-100°C for 0.5-15 min.
  • the thickness of the photosensitive resin layer is preferably 5-95 ⁇ m, more preferably 10-50 ⁇ m, and more preferably 15-30 ⁇ m. If the thickness of the photosensitive resin layer is less than 5 ⁇ m, the insulation is not good, and if the thickness of the photosensitive resin layer exceeds 95 ⁇ m, the resolution may be poor.
  • plastic films such as polyethylene terephthalate, polyethylene naphthalate, polypropylene, polyethylene, cellulose acetate, polyalkylmethacrylate Ester, methacrylate copolymer, polyvinyl chloride, polyvinyl alcohol, polycarbonate, polystyrene, cellophane, vinyl chloride copolymer, polyamide, polyimide, ethylene chloride-vinyl acetate copolymer, polytetramethylene Vinyl fluoride, polytrifluoroethylene and the like.
  • composite materials composed of two or more materials can also be used.
  • polyethylene terephthalate having excellent light penetration is used.
  • the thickness of the support is preferably 5-150 ⁇ m, and more preferably 10-50 ⁇ m.
  • the coating of the photosensitive resin composition is not particularly limited, and for example, a spray coating method, a drum coating method, a spin coating method, a slit coating method, a compression coating method, a curtain coating method, and a dye coating can be used Conventional methods such as cloth method, line coating method, blade coating method, roll coating method, blade coating method, spray coating method, dip coating method, etc.
  • the present invention provides the application of the above dry film in the manufacture of printed circuit boards, including:
  • Lamination step Laminating a photosensitive resin laminate on a copper-clad laminate or flexible substrate;
  • Exposure step Expose the photosensitive resin layer in the photosensitive resin laminate, and irradiate active light in the form of an image to photocur the exposed portion;
  • Conductor pattern forming process etching or plating the part of the surface of the copper-clad laminate or flexible substrate that is not covered by the protection pattern;
  • Peeling step peeling the protective pattern from the copper-clad laminate or flexible substrate.
  • the present invention provides the application of the above dry film in manufacturing a protective pattern, including the above-mentioned lamination step, exposure step and development step, the difference is that in the lamination step, the photosensitive resin laminate can be laminated on various materials On the substrate.
  • the present invention provides the application of the above dry film in manufacturing a conductor pattern, including the above-mentioned lamination step, exposure step, development step, and conductor pattern formation step, except that in the lamination step, the photosensitive resin laminate is laminated on the metal Board or metal-coated insulating board.
  • the present invention provides the application of the above-mentioned dry film in manufacturing a frame wire, including the above-mentioned lamination step, exposure step, development step, and conductor pattern forming step, except that the photosensitive resin laminate is laminated in the lamination step On the metal plate, the part not covered by the protection pattern is etched in the conductor pattern forming process.
  • the present invention provides the application of the above dry film in the manufacture of semiconductor packages, including the above-mentioned lamination step, exposure step, development step, and conductor pattern forming step, the difference is that in the lamination step, the photosensitive resin laminate is laminated on On a wafer with a large-scale integrated circuit, the part not covered by the protection pattern is plated in the conductor pattern forming process.
  • the photosensitive resin composition of the present invention can be directly applied on a substrate by a wet film method, and is used for the manufacture of printed circuit boards, protective patterns, conductor patterns, lead wires, semiconductor packages, and the like.
  • the photosensitive resin composition can be applied on the substrate by conventional methods such as roll coating, blade coating, spray coating, and dip coating, and dried to form the photosensitive resin layer.
  • the exposure may include a mask exposure method (a method in which a negative or positive mask pattern of a wiring pattern irradiates active light in the form of an image), a projection exposure method, or a direct imaging exposure method using laser, digital optic
  • a mask exposure method a method in which a negative or positive mask pattern of a wiring pattern irradiates active light in the form of an image
  • a projection exposure method or a direct imaging exposure method using laser, digital optic
  • the method of direct drawing exposure such as the processing exposure method, irradiates the active light in the form of an image.
  • a well-known light source such as a carbon arc lamp, a mercury vapor arc lamp, an ultra-high pressure indicator lamp, a high-pressure indicator lamp, a gas laser such as a xenon lamp, an argon laser, a solid laser such as a YAG laser, a semiconductor laser, and gallium nitride can be used It is a blue-violet laser and other light sources that effectively emit ultraviolet light.
  • a light source that efficiently emits visible light such as a floodlight for photography or a fluorescent lamp can also be used.
  • the photosensitive resin composition of the present invention is not particularly limited to the type of light source of active light, and the exposure amount is preferably 10-1000 mJ/cm 2 .
  • the unexposed portion of the photosensitive resin layer is removed with a developer.
  • the support When the support is present on the photosensitive resin layer, the support can be removed by an automatic peeler, etc., and then the unexposed portion can be removed using a developer such as an alkaline aqueous solution, an aqueous developer, or an organic solvent.
  • a developer such as an alkaline aqueous solution, an aqueous developer, or an organic solvent.
  • the alkaline aqueous solution may be 0.1-5 mass% sodium carbonate solution, 0.1-5 mass% potassium carbonate solution, 0.1-5 mass% sodium hydroxide solution, etc.
  • the pH value is preferably 9-11.
  • Surfactants, defoamers, organic solvents, etc. can also be added to the alkaline aqueous solution.
  • the development method may be conventional methods such as dipping, spraying, and brushing.
  • the conductor layer of the uncovered circuit-forming substrate is etched away to form a conductor pattern.
  • the etching method can be selected according to the conductor layer to be removed.
  • examples of the etching solution include copper oxide solution, iron oxide solution, alkali etching solution, hydrogen peroxide-based etching solution, and the like.
  • plating process using the resist pattern formed on the substrate as a mask, copper, solder, or the like is plated on the insulating plate of the uncovered circuit-forming substrate. After the plating process, the resist pattern is removed to form a conductor pattern.
  • plating treatment plating treatment or electroless plating treatment may be used, and electroless plating treatment is preferable.
  • Examples of the electroless plating treatment include copper plating such as copper sulfate plating and copper pyrophosphate plating, high-throw solder plating and other solder plating, and watt bath (nickel sulfate-chloride) Nickel) plating and nickel sulfamate plating and other nickel plating, hard gold plating and soft gold plating and other gold plating.
  • copper plating such as copper sulfate plating and copper pyrophosphate plating, high-throw solder plating and other solder plating, and watt bath (nickel sulfate-chloride) Nickel) plating and nickel sulfamate plating and other nickel plating, hard gold plating and soft gold plating and other gold plating.
  • the resist pattern can be removed by an aqueous solution that is more alkaline than the alkaline aqueous solution used in the development step.
  • an aqueous solution that is more alkaline than the alkaline aqueous solution used in the development step.
  • a strong alkaline aqueous solution for example, a 1-10% by mass sodium hydroxide aqueous solution can be used.
  • Figure 1 is a high performance liquid chromatogram of Comparative Product 1.
  • Figure 2 is a schematic diagram of the structure of two linking compounds in BCIM.
  • Figure 3 is a high performance liquid chromatogram of Comparative Product 2.
  • Figure 5 is a high performance liquid chromatogram of product 1.
  • Figure 6 is a high performance liquid chromatogram of product 2.
  • Figure 7 is a comparison of the sensitivity test results of product 1-2 and comparative product 1-3.
  • Comparative product 1 was detected using high performance liquid chromatography and single crystal diffraction.
  • Figure 1 is a high performance liquid chromatogram of Comparative Product 1, showing that the main component of Comparative Product 1 accounts for 82.52% of the total.
  • the main component of product 1 has only one peak in the liquid phase, single crystal diffraction analysis of the separated single main component revealed two peak shapes. Combined with structural characteristics, it can be determined that the main product of the coupling of two monoimidazoles is a mixture of N containing hydrogen on one imidazole and C at the 2-position on the other imidazole. Three-dimensional structure, the structure is shown as the 1-2' and 2'-3 connection sites described in the present invention.
  • Comparative Product 1 is composed of two compounds with 1-2' and 3-2' linking sites.
  • the structural formulas are as follows:
  • the difference is that after obtaining the comparative product 1, the beating process is performed, the beating liquid used is a mixed solution of toluene and water, the ratio of toluene and water is 1:4, the weight of the beating liquid and product 1 The ratio is 1:1.
  • the product 2 is obtained by centrifugation, suction filtration and drying.
  • the comparison product 2 was detected using high performance liquid chromatography. The results showed that the main components of the comparative product 2 (compounds of the structure represented by formula (I) and formula (II)) accounted for 86.18% of the total of the comparative product 2 (see FIG. 3).
  • the difference is that the beating liquid used is methanol, and the weight ratio of the beating liquid to product 1 is 1:1. After beating, centrifugation, suction filtration, and drying obtain the comparative product 3.
  • the test results show that the main components of the comparative product 3 (compounds of structures represented by formula (I) and formula (II)) account for 92.10% of the total of the comparative product 3 (see FIG. 4).
  • the difference is that after the comparative product 1 is obtained, recrystallization treatment is carried out (the temperature is increased after refluxing and stirring, and then the temperature is reduced to crystallize). 1.2:1, centrifuge, rinse and dry after cooling to get product 1.
  • the test result shows that the main component of the product 1 (the compound represented by the formula (I) and formula (II)) accounts for 97.45% of the total product 1 (see FIG. 5).
  • the recrystallization solution used is a mixed solvent of toluene and methanol, the ratio of toluene and methanol is 1:1, the weight ratio of the recrystallization solution and product 1 is 1.2:1, centrifugation after cooling ⁇ Suction filtration and drying to obtain product 5.
  • the test result shows that the main component of the product 2 (the compound represented by the formula (I) and formula (II)) accounts for 99.27% of the total product 2 (see FIG. 6).
  • the difference is that the phase transfer catalyst used is 18-crown-6, and finally the product 3 is obtained.
  • the detection result shows that the main component of the product 3 (the compound represented by formula (I) and formula (II)) accounts for 97.23% of the total product 3.
  • the beating liquid used is a mixed solution of toluene and methanol.
  • the ratio of toluene to methanol is 1:1.
  • the weight of the beating liquid and product 1 The ratio is 0.6:1.
  • the product 4 is obtained by centrifugation, suction filtration and drying.
  • the test result shows that the main component of the product 4 (the compound represented by formula (I) and formula (II)) accounts for 98.67% of the total product 4.
  • the test result shows that the main component of the product 5 (the compound represented by the formula (I) and formula (II)) accounts for 99.41% of the total product 5.
  • the photosensitive resin compositions of Examples 1-2 and Comparative Examples 1-3 were uniformly mixed to test the sensitivity.
  • the dosage unit of each component in the table is g.
  • TMPTA was purchased from Tianjin Beilian Fine Chemical Development Co., Ltd.
  • NPG was purchased from Shenzhen Pengshunxing Technology Co., Ltd.
  • PGMEA was purchased from Jinan Huifengda Chemical Co., Ltd.
  • the peak value represents the maximum heat dissipation, mw/mg, the greater the heat dissipation, the higher the sensitivity.
  • the slope represents the curing rate, the smaller the slope, the higher the sensitivity.
  • the sensitivity test result is: Comparative product 1 ⁇ Comparative product 2 ⁇ Comparative product 3 ⁇ Product 1 ⁇ Product 2.
  • the results show that the sensitivity of the BCIM mixed photoinitiator after application is closely related to the content of the two compounds of formula (I) and formula (II). As the proportion of both in BCIM is gradually increased, the overall sensitivity is increased accordingly, especially when the content is higher than 97%, the exotherm of BCIM reaches 12mw/mg, which can meet the requirements of dry film for exposure time.
  • the sensitivity of the photoinitiator determines the exposure time of the dry film, and the exposure time is a very important factor affecting the dry film image.
  • the total content of the compounds of formula (I) and formula (II) in the BCIM mixed photoinitiator of the present invention is preferably 97% or more, and more preferably 99% or more.
  • the photosensitive resin composition was sufficiently stirred, and it was evenly coated on the surface of a 25 ⁇ m thick polyethylene terephthalate film as a support using a bar coater, and dried in a dryer at 95° C. for 5 minutes. A photosensitive resin layer with a thickness of 40 ⁇ m was formed, and then a 15 ⁇ m-thick polyethylene film as a protective layer was laminated on the surface of the photosensitive resin layer where no polyethylene terephthalate film was laminated to obtain a dry film.
  • a 1.2-mm-thick copper-clad laminate laminated with a 35- ⁇ m-thick rolled copper foil was used, and the surface was subjected to wet polishing roll grinding (Scotch-Brite (registered trademark) HD#600 manufactured by 3M Corporation, and passed twice ).
  • the polyethylene film protective layer was peeled off from the dry film, and then using a hot roll laminator (AL-70 manufactured by Asahi Kasei Co., Ltd.), it was laminated on a copper clad preheated to 60°C at a roll temperature of 105°C. Laminate.
  • the gas pressure is 0.35 MPa, and the lamination speed is 1.5 m/min.
  • the mask was placed on a polyethylene terephthalate film as a support, and exposed through an ultra-high pressure mercury lamp (HMW-201KB manufactured by ORCMANUFACTURINGCO., LTD.).
  • HMW-201KB manufactured by ORCMANUFACTURINGCO., LTD.
  • the polyethylene terephthalate film was peeled off, and a 1% by mass Na 2 CO 3 aqueous solution at 30° C. was sprayed on the photosensitive resin layer using an alkali developing machine (developer for dry film manufactured by FujiKiko Co., Ltd.) Above, the unexposed portion of the photosensitive resin layer is dissolved and removed in a time twice as long as the minimum development time.
  • the minimum development time is the shortest time required to completely dissolve the photosensitive resin layer of the unexposed portion.
  • the photosensitive resin composition was sufficiently stirred, and the composition was uniformly coated on the surface of a 25 ⁇ m-thick polyethylene terephthalate film as a support using a bar coater. Dry in a dryer at 95°C for 5 min to form a photosensitive resin layer. Then the surface of the photosensitive resin layer was visually inspected and graded as follows:
  • the photosensitive resin layer was exposed for 15 minutes using a 21-stage stepped exposure meter manufactured by Stouffer with a 21-stage brightness change from transparent to black to evaluate its sensitivity. After the exposure, development is carried out at twice the minimum development time, and according to the exposure amount of the stepped exposure table with the resist film completely remaining being 8, the following classification is performed:
  • the exposure is 20mJ/cm 2 or less
  • the exposure is 20mJ/cm 2 -50mJ/cm 2 , excluding the end value;
  • the exposure is 50mJ/cm 2 or more.
  • the resolution of the dry film was measured.
  • the resolution is the minimum value of the pattern after the unexposed portion is cleaned out of the resist pattern formed by development after exposure.
  • the resolution value is 30 ⁇ m-50 ⁇ m, excluding the end value
  • ⁇ The resolution value is above 50 ⁇ m.
  • the hydrophilicity was evaluated by the amount of precipitation after the photosensitive resin layer was dissolved.
  • the photosensitive resin composition was sufficiently stirred, and applied uniformly on the surface of a 25 ⁇ m-thick polyethylene terephthalate film as a support using a bar coater. Dry in a dryer at 95°C for 4 minutes to form a photosensitive resin layer with a layer thickness of approximately 30.5 ⁇ m and a layer weight of approximately 3.2 g.
  • 0 precipitation amount is less than 0.005g
  • 5 Medium amount of light yellow substance (usually fine), the amount of precipitation is between 0.05-0.08g;
  • the developability is evaluated according to the following criteria:
  • the BCIM mixed photoinitiator of the present invention has excellent compatibility when applied to a photosensitive resin composition, the composition has high sensitivity, and good resolution, hydrophilicity, and developability. Compared with the photosensitive resin compositions of Comparative Examples 4-6, the present invention has significantly improved performance in terms of sensitivity, resolution, and hydrophilicity.

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Abstract

Cette invention concerne un photo-initiateur hybride à base de 2,2'-bis(o-chlorophényl-4,4',5,5'-tétraphényldiimidazole, qui contient un composé selon la formule (I) ayant une position de liaison 1-2' et un composé selon la formule (II) ayant une position de liaison 2'-3, et la somme de la teneur des deux composés représentant 97 % ou plus du photo-initiateur hybride. Le photo-initiateur hybride à base de 2,2'-bis(o-chlorophényl) -4,4',5,5'-tétraphényldiimidazole a une excellente photosensibilité et une bonne résolution après avoir été appliqué à une composition de résine photosensible, il peut être largement utilisé dans la fabrication de cartes de circuits imprimés, de motifs de protection, de tracés conducteurs, de grilles de connexion, de boîtiers de semi-conducteurs, etc., au moyen d'un film sec et d'un film humide.
PCT/CN2019/120523 2018-11-30 2019-11-25 Photo-initiateur hybride à base d'hexaarylbiimidazole Ceased WO2020108420A1 (fr)

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KR1020217020297A KR102542061B1 (ko) 2018-11-30 2019-11-25 헥사아릴비스이미다졸 혼합 광개시제
JP2021530322A JP7680744B2 (ja) 2018-11-30 2019-11-25 ヘキサアリールビスイミダゾール混合光開始剤
MYPI2021002957A MY204061A (en) 2018-11-30 2019-11-25 Hexaarylbiimidazole hybrid photoinitiator

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CN201811451251.6A CN111258181B (zh) 2018-11-30 2018-11-30 六芳基双咪唑混合光引发剂
CN201811451251.6 2018-11-30

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WO2020108420A1 true WO2020108420A1 (fr) 2020-06-04

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113929624A (zh) * 2020-07-13 2022-01-14 常州强力电子新材料股份有限公司 一种吡唑啉类化合物、感光性树脂组合物及图形化方法

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111752099B (zh) * 2019-03-29 2022-03-22 常州强力电子新材料股份有限公司 感光性树脂组合物及应用、彩色滤光片及图像显示装置
CN112062721B (zh) * 2019-05-23 2023-06-30 常州正洁智造科技有限公司 能够提升体系稳定性的habi类光引发剂及其应用
CN115128899A (zh) * 2021-03-26 2022-09-30 常州正洁智造科技有限公司 一种具有提升的体系色相稳定性的感光性树脂组合物
KR20250020401A (ko) * 2022-04-02 2025-02-11 항저우 퍼스트 일렉트로닉 머티리얼 컴퍼니 리미티드 드라이 필름 레지스트, 감광성 드라이 필름 및 동박 적층판

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA824633A (en) * 1969-10-07 E.I. Du Pont De Nemours And Company Photopolymerizable products and processes
US3549367A (en) * 1968-05-24 1970-12-22 Du Pont Photopolymerizable compositions containing triarylimidazolyl dimers and p-aminophenyl ketones
CN1043797A (zh) * 1988-12-23 1990-07-11 纳幕尔杜邦公司 用于光聚合组合物的可见光增感剂
JP2001222106A (ja) * 2000-02-08 2001-08-17 Hitachi Chem Co Ltd 感光性樹脂組成物、これを用いた感光性エレメント、レジストパターンの製造法、プリント配線板の製造法
CN101379434A (zh) * 2006-02-08 2009-03-04 日合·莫顿株式会社 感光性树脂组合物及使用该组合物的光刻胶膜
CN102227685A (zh) * 2008-12-02 2011-10-26 伊斯曼柯达公司 用于改善平版印刷版的成像和非成像区域的划痕敏感性的具有纳米颗粒的上胶组合物
CN102675210A (zh) * 2012-05-23 2012-09-19 湖南和诚医药化学品有限公司 一种双咪唑光引发剂的制备方法
CN110114376A (zh) * 2017-03-31 2019-08-09 株式会社Adeka 固化性组合物、固化物的制造方法、其固化物、及使用其的粘接剂

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1072447A (ja) * 1996-06-24 1998-03-17 Nippon Kayaku Co Ltd ヘキサアリールビスイミダゾール類の製造方法
JPH1036354A (ja) * 1996-07-19 1998-02-10 Nippon Kayaku Co Ltd ヘキサアリールビスイミダゾール類の製造方法
JP3867177B2 (ja) * 1997-04-30 2007-01-10 Ｊｓｒ株式会社 カラーフィルタ用感放射線性組成物
US6180319B1 (en) * 1998-03-11 2001-01-30 E. I. Du Pont De Nemours And Company Process for the continuous liquid processing of photosensitive compositions having reduced levels of residues
JP4393051B2 (ja) * 2002-10-15 2010-01-06 昭和電工株式会社 ヘキサアリールビイミダゾール化合物およびそれを含む光重合開始剤組成物
JP4675693B2 (ja) * 2005-06-23 2011-04-27 東京応化工業株式会社 感光性樹脂組成物
CN101302257A (zh) * 2008-06-03 2008-11-12 江南大学 一种紫外光敏复合引发体系及其应用
JP2009294538A (ja) 2008-06-06 2009-12-17 Hitachi Chem Co Ltd 感光性樹脂組成物及び感光性エレメント
JP2010122381A (ja) * 2008-11-18 2010-06-03 Hitachi Chem Co Ltd 黒色感光性樹脂組成物、ブラックマトリクスの製造方法、カラーフィルタの製造方法及びカラーフィルタ
CN101418051A (zh) * 2008-12-01 2009-04-29 常州强力电子新材料有限公司 一种含有不对称性六芳基双咪唑光引发剂及其制备方法
JP2010256532A (ja) 2009-04-23 2010-11-11 Hitachi Chem Co Ltd 感光性樹脂組成物、感光性エレメント及びこれを用いたレジストパターンの形成方法
JP2015087429A (ja) * 2013-10-28 2015-05-07 日立化成株式会社 感光性樹脂組成物、感光性エレメント及びレジストパターンの形成方法
JP6755109B2 (ja) * 2016-03-29 2020-09-16 旭化成株式会社 感光性樹脂組成物、感光性樹脂積層体、レジストパターン形成方法及び導体パターン製造方法

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA824633A (en) * 1969-10-07 E.I. Du Pont De Nemours And Company Photopolymerizable products and processes
US3549367A (en) * 1968-05-24 1970-12-22 Du Pont Photopolymerizable compositions containing triarylimidazolyl dimers and p-aminophenyl ketones
CN1043797A (zh) * 1988-12-23 1990-07-11 纳幕尔杜邦公司 用于光聚合组合物的可见光增感剂
JP2001222106A (ja) * 2000-02-08 2001-08-17 Hitachi Chem Co Ltd 感光性樹脂組成物、これを用いた感光性エレメント、レジストパターンの製造法、プリント配線板の製造法
CN101379434A (zh) * 2006-02-08 2009-03-04 日合·莫顿株式会社 感光性树脂组合物及使用该组合物的光刻胶膜
CN102227685A (zh) * 2008-12-02 2011-10-26 伊斯曼柯达公司 用于改善平版印刷版的成像和非成像区域的划痕敏感性的具有纳米颗粒的上胶组合物
CN102675210A (zh) * 2012-05-23 2012-09-19 湖南和诚医药化学品有限公司 一种双咪唑光引发剂的制备方法
CN110114376A (zh) * 2017-03-31 2019-08-09 株式会社Adeka 固化性组合物、固化物的制造方法、其固化物、及使用其的粘接剂

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113929624A (zh) * 2020-07-13 2022-01-14 常州强力电子新材料股份有限公司 一种吡唑啉类化合物、感光性树脂组合物及图形化方法

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