WO2020108420A1 - Hexaarylbisimidazole hybrid photoinitiator - Google Patents

Hexaarylbisimidazole hybrid photoinitiator 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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PCT/CN2019/120523
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French (fr)
Chinese (zh)
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钱彬
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常州格林感光新材料有限公司
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Priority to JP2021530322A priority Critical patent/JP2022509242A/en
Priority to KR1020217020297A priority patent/KR102542061B1/en
Publication of WO2020108420A1 publication Critical patent/WO2020108420A1/en

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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.

Abstract

Disclosed is a 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyldiimidazole hybrid photoinitiator, which contains a compound of formula (I) having a 1-2' connection position and a compound of formula (II) having a 2'-3 connection position, and the sum of the content of the two compounds accounts for 97% or more of the hybrid photoinitiator. The 2,2'-bis(o-chlorophenyl) -4,4',5,5'-tetraphenyldiimidazole hybrid photoinitiator has an excellent photosensibility and a good resolution after being applied to a photosensitive resin composition, which can be widely used in the manufacture of printed circuit boards, protective patterns, conductor patterns, lead frames, semiconductor packages, etc., by means of a dry film and a wet film.

Description

六芳基双咪唑混合光引发剂Hexaarylbisimidazole mixed photoinitiator 技术领域Technical field
本发明属于有机化学领域，具体涉及一种2,2'-二(邻氯苯基)-4,4',5,5'-四苯基二咪唑混合光引发剂、含有该引发剂的感光性树脂组合物及其应用。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.
背景技术Background technique
近年来随着个人电脑等精密电子设备上所使用的印刷线路板的微小化，使得具有高感光度、高解像性及分辨率的感光性树脂组合物成为研究的热点。而光引发剂作为感光性树脂组合物中必不可少的组分之一，要求其具有高的引发效率、与体系具有较好的相容性和好的溶解性等优异性能。在自由基聚合体系中，由于六芳基双咪唑类化合物具有特殊的化学结构，在紫外光的作用下可以光解产生大分子自由基，因而成为了感光性树脂组合物中非常重要的光引发剂。In recent years, with the miniaturization of printed wiring boards used in personal computers and other precision electronic equipment, photosensitive resin compositions with high sensitivity, high resolution, and resolution have become a hot spot for research. As one of the indispensable components in the photosensitive resin composition, the photoinitiator is required to have high initiation efficiency, good compatibility with the system, good solubility and other excellent properties. In 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.
在六芳基双咪唑类光引发剂中，2,2'-二(邻氯苯基)-4,4',5,5'-四苯基二咪唑(BCIM)应用最为广泛。BCIM存在多种连接位的异构体，现有市场的BCIM基本上是由多种连接位的异构体混合而成。目前已报道的BCIM在感光性树脂组合物中的应用均未对内部异构体组成和含量做进一步要求，仅是将BCIM混合物直接应用于组合物中。但是，市场上不同厂家生产的BCIM应用性能差异很大，给下游生产厂家带来很大的困惑。Among the hexaarylbisimidazole photoinitiators, 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyldiimidazole (BCIM) is the most widely used. There are multiple isomers of BCIM. The existing market BCIM is basically a mixture of isomers of multiple positions. At present, the reported application of BCIM in photosensitive resin compositions does not further require the internal isomer composition and content, but only applies the BCIM mixture directly to the composition. However, the performance of BCIM applications produced by different manufacturers on the market varies greatly, which causes great confusion to downstream manufacturers.
申请人的研发团队在研究六芳基双咪唑类光引发剂中的2,2',5-三(邻-氯苯基)-4-(3,4-二甲氧基苯基)-4',5'-二苯基二咪唑(TCDM-HABI)与2,2',4,4'-四(邻-氯苯基)-5,5'-二(3,4-二甲氧基苯基)二咪唑(TCTM-HABI)时，意外 发现连接位及特定连接位下的含量对引发剂的感光度有明显影响。因此，在此研究基础上探究异构体的结构和含量对BCIM混合光引发剂性能的影响是进一步提高BCIM实际应用性能的一种有效手段。The applicant's R&D team is studying 2,2',5-tris(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4 in hexaarylbisimidazole photoinitiators ',5'-diphenyldiimidazole (TCDM-HABI) and 2,2',4,4'-tetra(o-chlorophenyl)-5,5'-bis(3,4-dimethoxy When phenyl)diimidazole (TCTM-HABI), it was unexpectedly found that the content of the connection site and the specific connection site has a significant effect on the sensitivity of the initiator. Therefore, to explore the effect of isomer structure and content on the performance of BCIM mixed photoinitiator based on this research is an effective way to further improve the practical application performance of BCIM.
发明内容Summary of the invention
不同连接位的BCIM性能差异很大，特别是在溶解性和感光度方面，而现有市场的BCIM由于组分不稳定且差异性大，导致性能不一，影响客户使用。针对现有技术的不足，本发明的目的首先在于提供一种BCIM混合光引发剂，含有特定连接位的异构体。相比于现有BCIM产品，本发明的光引发剂具有稳定且优异的应用性能，在感光度等方面优势明显。The performance of BCIM at different connection sites varies greatly, especially in terms of solubility and sensitivity. However, due to the unstable components and large differences in BCIM in the existing market, the performance varies, which affects the use of customers. In view of the shortcomings of the prior art, 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.
具体来说，本发明的2,2'-二(邻氯苯基)-4,4',5,5'-四苯基二咪唑混合光引发剂，主要含有具有1-2’连接位的式(I)化合物和具有2’-3连接位的式(II)化合物，且两种化合物的含量之和占该混合光引发剂的97％以上，Specifically, 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,
Figure PCTCN2019120523-appb-000001
Figure PCTCN2019120523-appb-000001
本发明的另一个目的在于提供包含上述2,2'-二(邻氯苯基)-4,4',5,5'-四苯基二咪唑混合光引发剂的感光性树脂组合物以及该组合物在光固化领域中的应用。Another object of the present invention is to provide 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.
本发明的2,2'-二(邻氯苯基)-4,4',5,5'-四苯基二咪唑混合光引发剂应用于 感光性树脂组合物后感光度优异、分辨率佳，能够通过干膜和湿膜的方式在制造印刷电路板、保护图案、导体图案、引框线、半导体封装等方面得到广泛应用。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.
发明详述Detailed description of the invention
基于本发明的目的，以下对各方面进行更详细的说明。Based on the purpose of the present invention, each aspect will be described in more detail below.
<2,2'-二(邻氯苯基)-4,4',5,5'-四苯基二咪唑混合光引发剂><2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyldiimidazole mixed photoinitiator>
本发明的2,2'-二(邻氯苯基)-4,4',5,5'-四苯基二咪唑混合光引发剂，含有具有1-2’连接位的式(I)化合物和具有2’-3连接位的式(II)化合物，且两种化合物的含量之和占该混合光引发剂的97％以上，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,
Figure PCTCN2019120523-appb-000002
Figure PCTCN2019120523-appb-000002
进一步地，上述式(Ⅰ)和(Ⅱ)两种化合物的含量之和占该混合光引发剂的99％以上。Further, the sum of the contents of the two compounds of the above formulas (I) and (II) accounts for more than 99% of the mixed photoinitiator.
本发明的2,2'-二(邻氯苯基)-4,4',5,5'-四苯基二咪唑混合光引发剂中，对式(Ⅰ)化合物和式(Ⅱ)化合物两者之间的比例没有特别限定，只要两者含量之和满足上述要求即可达到本发明的目的。In the 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyldiimidazole mixed photoinitiator of the present invention, the compound of formula (I) and the compound of formula (II) The ratio between the two is not particularly limited, as long as the sum of the two contents meets the above requirements to achieve the object of the present invention.
除了上述式(Ⅰ)和(Ⅱ)两种化合物之外，2,2’-二(邻-氯苯基)-4,4’,5,5’-四苯基二咪唑(BCIM)还有1-4’、1-5’、3-4’、3-5’、1-1’、1-3’、3-3’等连 接位的异构体，但只有满足本发明结构和含量要求的2,2'-二(邻氯苯基)-4,4',5,5'-四苯基二咪唑混合光引发剂才能表现出最优的感光度。相比而言，当两者含量之和低于97％时，BCIM的感光度有明显变低的趋势。本文中，BCIM混合光引发剂中的组分含量由高效液相色谱仪检测。In addition to the two compounds of formulas (I) and (II) above, 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyldiimidazole (BCIM) 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. In contrast, when the sum of the two contents is less than 97%, the sensitivity of BCIM tends to be significantly lower. In this paper, the content of the components in the BCIM mixed photoinitiator is detected by high performance liquid chromatography.
2,2'-二(邻氯苯基)-4,4',5,5'-四苯基二咪唑的合成方法是光刻胶领域公知的一类光引发剂，可通过取代三苯基咪唑类化合物的氧化偶合来制备，反应所用的氧化剂可以举例如：次氯酸钠、铁***等，所用相转移催化剂可以举例如：四丁基溴化铵、苄基三乙基氯化铵、冠醚(15-冠醚-5、18-冠醚-6)、聚乙二醇等，具体制备工艺可参照例如US3784557、US4622286和US4311783等现有技术中的记载(在此将其全文引入以作为参考)。通过现有的技术工艺得到的2,2'-二(邻氯苯基)-4,4',5,5'-四苯基二咪唑中，上述式(Ⅰ)和(Ⅱ)两种化合物的含量之和占BCIM混合光引发剂的含量偏低，其杂质成分主要为其他连接位的二咪唑化合物，在现有工艺的基础上，增加溶剂打浆或重结晶工艺，即可方便地获得满足本发明组成要求的2,2'-二(邻氯苯基)-4,4',5,5'-四苯基二咪唑混合光引发剂。所述溶剂可以是甲苯、纯苯、甲醇、乙醇、乙酸乙酯、二氯甲烷、水中的一种或两种以上的组合物。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. For the specific preparation process, please refer to the descriptions in the prior art such as US3784557, US4622286 and US4311783 (the entire contents of which are hereby incorporated as reference). In 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyldiimidazole obtained by the existing technical process, the two compounds of the above formulas (I) and (II) The sum of the content of BCIM mixed photoinitiator is relatively low, and its impurity component is mainly the diimidazole compound of other connection sites. On the basis of the existing process, adding solvent beating or recrystallization process can easily meet the content The 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.
<感光性树脂组合物><Photosensitive resin composition>
本发明还涉及包含上述2,2'-二(邻氯苯基)-4,4',5,5'-四苯基二咪唑混合光引发剂的感光性树脂组合物。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.
代表性地，除上述2,2'-二(邻氯苯基)-4,4',5,5'-四苯基二咪唑混合光引发剂之外，所述组合物还包含：碱可溶性聚合物，具有烯属不饱和双键的化合物，其它光引发剂和/或增感剂，以及任选的助剂。Typically, in addition to 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.
以下对各组分做进一步详细说明。Each component will be described in further detail below.
2,2'-二(邻氯苯基)-4,4',5,5'-四苯基二咪唑混合光引发剂2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyldiimidazole mixed photoinitiator
在本发明的感光性树脂组合物中，组分2,2'-二(邻氯苯基)-4,4',5,5'-四苯基二咪唑混合光引发剂如上文所示。In the photosensitive resin composition of the present invention, the component 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyldiimidazole mixed photoinitiator is as shown above.
在100质量份的感光性树脂组合物中，2,2'-二(邻氯苯基)-4,4',5,5'-四苯基二咪唑混合光引发剂的含量优选为1-10质量份。此含量范围内，2,2'-二(邻氯苯基)-4,4',5,5'-四苯基二咪唑混合光引发剂在表现出优异感光活性和分辨率的同时，兼具更好的体系相容性。In 100 parts by mass of the photosensitive resin composition, 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.
碱可溶性聚合物Alkali soluble polymer
碱可溶性聚合物可赋予感光性树脂组合物成膜功能。作为碱可溶性聚合物，只要是具有这样特性的聚合物就可以没有特别限制地适用。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.
示例性地，适用的碱可溶性聚合物可以是(甲基)丙烯酸系聚合物、苯乙烯系聚合物、环氧系聚合物、脂肪族聚氨酯(甲基)丙烯酸酯聚合物、芳香族聚氨酯(甲基)丙烯酸酯聚合物、酰胺系树脂、酰胺环氧系树脂、醇酸系树脂、以及酚醛系树脂等。Exemplarily, 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.
进一步地，碱可溶性聚合物可经由聚合性单体进行自由基聚合而得到。作为聚合性单体，可例举出：苯乙烯、乙烯基甲苯、α-甲基苯乙烯、对甲基苯乙烯、对乙基苯乙烯、对氯苯乙烯等在α-位或在芳香族环上被取代的可聚合的苯乙烯衍生物；丙烯酰胺、双丙酮丙烯酰胺等丙烯酰胺衍生物；丙烯腈、乙烯基正丁基醚等乙烯基醇的醚类衍生物；(甲基)丙烯酸、α-溴代(甲基)丙烯酸、α-氯代(甲基)丙烯酸、β-呋喃基(甲基)丙烯酸、β-苯乙烯基(甲基)丙烯酸等(甲基)丙烯酸衍生物；(甲基)丙烯酸烷基酯、(甲基)丙烯酸苄酯、甲基丙烯酸苯氧基乙酯、(甲基)丙烯酸四氢糠基酯、(甲基)丙烯酸二甲基氨基乙酯、(甲基)丙烯酸二乙基氨基乙酯、(甲基)丙烯酸缩水甘油酯、2,2,2-三氟 乙基(甲基)丙烯酸酯、2,2,3,3-四氟丙基(甲基)丙烯酸酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸四氢糠基酯、(甲基)丙烯酸二甲基氨基乙酯、(甲基)丙烯酸二乙基氨基乙酯、(甲基)丙烯酸缩水甘油酯等(甲基)丙烯酸酯类；马来酸、马来酸酐，马来酸单甲酯、马来酸单乙酯、马来酸单异丙酯等马来酸单酯；富马酸、肉桂酸、α-氰基肉桂酸、衣康酸、巴豆酸、丙醇酸、N-乙烯基己内酰胺；N-乙烯基吡咯烷酮等。这些聚合性单体可以单独使用，也可以两种以上组合使用。Further, the alkali-soluble polymer can be obtained by radical polymerization of a polymerizable monomer. Examples of the polymerizable monomer include styrene, vinyl toluene, α-methylstyrene, p-methylstyrene, p-ethylstyrene, p-chlorostyrene, etc. at the α-position or in the aromatic Polymerizable styrene derivatives substituted on the ring; acrylamide derivatives such as acrylamide and diacetone acrylamide; ether derivatives of vinyl alcohol such as acrylonitrile and vinyl n-butyl ether; (meth)acrylic acid , Α-bromo (meth) acrylic acid, α-chloro (meth) acrylic acid, β-furyl (meth) acrylic acid, β-styryl (meth) acrylic acid and other (meth) acrylic acid derivatives; Alkyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl methacrylate, tetrahydrofurfuryl (meth)acrylate, dimethylaminoethyl (meth)acrylate, ( Diethylaminoethyl methacrylate, glycidyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl ( Meth)acrylate, 2-ethylhexyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylamino (meth)acrylate (Meth)acrylates such as ethyl ester, glycidyl (meth)acrylate; maleic acid, maleic anhydride, monomethyl maleate, monoethyl maleate, monoisopropyl maleate, etc. Maleic acid monoester; fumaric acid, cinnamic acid, α-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.
进一步地，从碱显影性和密合性的角度考虑，优选使用含羧基的碱可溶性聚合物。具有羧基的碱可溶性聚合物可以为包含(甲基)丙烯酸作为单体单元的丙烯酸树脂，其通过使用(甲基)丙烯酸作为单体单元导入羧基；可以为除(甲基)丙烯酸以外进一步包含(甲基)丙烯酸烷基酯作为单体单元的共聚物；也可以为除(甲基)丙烯酸以外进一步含有除(甲基)丙烯酸和(甲基)丙烯酸烷基酯以外的聚合性单体(如，具有乙烯性不饱和基团的单体)作为单体成分的共聚物。Furthermore, from the viewpoint of alkali developability and adhesion, it is preferable to use a carboxyl group-containing alkali-soluble polymer. 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.
进一步地，含羧基的碱可溶性聚合物可通过具有羧基的聚合性单体与其它聚合性单体进行自由基聚合而得到，特别是由(甲基)丙烯酸酯、乙烯性不饱和羧酸和其他可共聚单体共聚而成的(甲基)丙烯酸酯系聚合物。所述的(甲基)丙烯酸酯可以是(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸己酯、(甲基)丙烯酸庚酯、(甲基)丙烯酸辛酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸壬酯、(甲基)丙烯酸癸酯、(甲基)丙烯酸十一烷基酯、(甲基)丙烯酸十二烷基酯、(甲基)丙烯酸环己酯、(甲基)丙烯酸苄基酯、(甲基)丙烯酸二乙胺基乙酯、(甲基)丙烯酸酯二甲胺基乙酯、(甲基)丙烯酸羟乙酯、(甲基)丙烯酸 羟丙酯、(甲基)丙烯酸糠基酯、(甲基)丙烯酸缩水甘油酯中的至少一种。所述的乙烯性不饱和羧酸优选是丙烯酸、甲基丙烯酸、丁烯酸、马来酸、富马酸、衣康酸中的至少一种，特别优选丙烯酸和/或甲基丙烯酸。所述的其他可共聚单体优选是(甲基)丙烯酰胺、(甲基)丙烯酸正丁酯、苯乙烯、乙烯基萘、(甲基)丙烯晴、乙酸乙烯基酯、乙烯基环己烷等中的至少一种。Further, 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, (meth)acrylic acid At least one of glycidyl esters. 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.
碱可溶性聚合物可以单独一种使用，也可以组合两种以上使用。作为组合两种以上使用的碱可溶性聚合物，可列举出由不同共聚成分构成的两种以上的碱可溶性聚合物、不同重均分子量的两种以上的碱可溶性聚合物、不同分散度的两种以上的碱可溶性聚合物等。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.
在本发明的感光性树脂组合物中，对碱可溶性聚合物的重均分子量没有特别限制，但从机械强度与碱显影性方面综合考虑，重均分子量优选为15000-200000，更优选为30000-150000，特别优选为30000-120000。当重均分子量大于15000时，曝光后耐显影液性有进一步提高的倾向，当该重均分子量小于200000时，显影时间有变得更短的倾向，且可以保持与光引发剂等其它组分的相容性。本文中，碱可溶性聚合物的重均分子量通过凝胶渗透色谱法(GPC)进行测定，通过使用标准聚苯乙烯的标准曲线进行换算而得到。In the photosensitive resin composition of the present invention, 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. When 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. Here, 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.
进一步地，从碱显影性良好的角度考虑，碱可溶性聚合物的酸值优选为50-300mgKOH/g，更优选为50-250mgKOH/g，进一步优选为70-250mgKOH/g，特别优选为100-250mgKOH/g。当碱可溶性树脂的酸值低于50mgKOH/g时，难以确保充分的显影速度，当超过300mgKOH/g时，密合性减小，容易发生图案短路，且易出现组合物贮存稳定性降低、粘度上升的问题。Further, from the viewpoint of good alkali developability, 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. When the acid value of the alkali-soluble resin is less than 50 mgKOH/g, it is difficult to ensure a sufficient development speed. When 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.
碱可溶性树脂的分子量分布[重均分子量(Mw)/数均分子量(Mn)]优选为1.5-6.0，特别优选为1.8-3.7。当分子量分布处于所述范围时，显影性优异。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.
以感光性树脂组合物总量100质量份计，碱可溶性聚合物在组合物中的含量优选是20-70质量份，更优选是30-60质量份。当碱可溶性聚合物的含量在20质量份以上，可确保感光性树脂组合物对于镀敷处理、蚀刻处理等的耐久性得到提高，当含量在70质量份以下，有利于提高感光性树脂组合物的灵敏度。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. When 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.
具有烯属不饱和双键的化合物Compounds with ethylenically unsaturated double bonds
具有烯属不饱和双键的化合物可促进感光性树脂组合物成膜。The compound having an ethylenically unsaturated double bond can promote the film formation of the photosensitive resin composition.
对具有烯属不饱和双键的化合物的种类没有特定的限制，只要是在分子内具有至少一个乙烯性不饱和键的光聚合性化合物即可。示例性地，可列举出如：α,β-不饱和羧酸与多元醇反应而得的化合物、双酚A类(甲基)丙烯酸酯化合物、α,β-不饱和羧酸与含缩水甘油基的化合物反应而得的化合物、分子内具有氨酯键的(甲基)丙烯酸酯化合物等氨基甲酸酯单体、壬基苯氧基亚乙基氧基(甲基)丙烯酸酯、壬基苯氧基八亚乙基氧基(甲基)丙烯酸酯、γ-氯-β-羟基丙基-β'-(甲基)丙烯酰氧基乙基-邻苯二甲酸酯、β-羟基乙基-β'-(甲基)丙烯酰氧基乙基-邻苯二甲酸酯、β-羟基丙基-β'-(甲基)丙烯酰氧基乙基-邻苯二甲酸酯、苯二甲酸类化合物、(甲基)丙烯酸烷基酯等。这些化合物可以单独使用，也可两种以上组合使用。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 α,β-unsaturated carboxylic acids with polyols, bisphenol A (meth)acrylate compounds, α,β-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, γ-chloro-β-hydroxypropyl-β'-(meth)acryloyloxyethyl-phthalate, β-hydroxyl Ethyl-β'-(meth)acryloyloxyethyl-phthalate, β-hydroxypropyl-β'-(meth)acryloyloxyethyl-phthalate , Phthalic acid compounds, alkyl (meth)acrylate, etc. These compounds may be used alone or in combination of two or more.
作为上述α,β-不饱和羧酸与多元醇反应而得的化合物，示例性地可以列举出：亚乙氧基数为2-14的聚乙二醇二(甲基)丙烯酸酯、亚丙氧基数为2-14的聚丙二醇二(甲基)丙烯酸酯、亚乙氧基数为2-14且亚丙氧基数为2-14的聚亚乙氧基·聚亚丙氧基二醇二(甲基)丙烯酸酯、三羟甲基丙烷二(甲基)丙烯酸 酯、三羟甲基丙烷三(甲基)丙烯酸酯、EO改性三羟甲基丙烷三(甲基)丙烯酸酯、PO改性三羟甲基丙烷三(甲基)丙烯酸酯、EO,PO改性三羟甲基丙烷三(甲基)丙烯酸酯、四羟甲基甲烷三(甲基)丙烯酸酯、四羟甲基甲烷四(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯聚丙二醇单(甲基)丙烯酸酯、聚乙二醇单(甲基)丙烯酸酯、三丙二醇二(甲基)丙烯酸酯等。这些化合物可以单独使用，也可两种以上组合使用。这里，“EO”表示环氧乙烷，经EO改性的化合物是指具有氧化乙烯基的嵌段结构的化合物；“PO”表示环氧丙烷，经PO改性的化合物是指具有氧化丙烯基的嵌段结构的化合物。As the compound obtained by reacting the above-mentioned α,β-unsaturated carboxylic acid with a polyhydric alcohol, for example, polyethylene glycol di(meth)acrylate having 2 to 14 ethyleneoxy groups and propylene oxide can be exemplified. Polypropylene glycol di(meth)acrylate with a base number of 2-14, polyethyleneoxy with a number of 2-14 and a propylene oxide with a number of 2-14 Group) acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, EO modified trimethylolpropane tri(meth)acrylate, PO modified Trimethylolpropane tri(meth)acrylate, EO, PO modified trimethylolpropane tri(meth)acrylate, tetramethylolmethane tri(meth)acrylate, tetramethylolmethane tetra (Meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate polypropylene glycol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate, tripropylene glycol Di (meth) acrylate and so on. These compounds may be used alone or in combination of two or more. Here, "EO" means ethylene oxide, and the EO-modified compound means a compound having a block structure of ethylene oxide; "PO" means propylene oxide, the PO-modified compound means having an oxypropylene group Block structure of the compound.
作为上述双酚A类(甲基)丙烯酸酯化合物，示例性地可以列举出如：2,2-双(4-((甲基)丙烯酰氧基多乙氧基)苯基)丙烷、2,2-双(4-((甲基)丙烯酰氧基多丙氧基)苯基)丙烷、2,2-双(4-((甲基)丙烯酰氧基多丁氧基)苯基)丙烷、2,2-双(4-((甲基)丙烯酰氧基多乙氧基多丙氧基)苯基)丙烷等。作为上述2,2-双(4-((甲基)丙烯酰氧基多乙氧基)苯基)丙烷，示例性地可以列举出如：2,2-双(4-((甲基)丙烯酰氧基二乙氧基)苯基)丙烷、2,2-双(4-((甲基)丙烯酰氧基三乙氧基)苯基)丙烷、2,2-双(4-((甲基)丙烯酰氧基四乙氧基)苯基)丙烷、2,2-双(4-((甲基)丙烯酰氧基五乙氧基)苯基)丙烷、2,2-双(4-((甲基)丙烯酰氧基六乙氧基)苯基)丙烷、2,2-双(4-((甲基)丙烯酰氧基七乙氧基)苯基)丙烷、2,2-双(4-((甲基)丙烯酰氧基八乙氧基)苯基)丙烷、2,2-双(4-((甲基)丙烯酰氧基九乙氧基)苯基)丙烷、2,2-双(4-((甲基)丙烯酰氧基十乙氧基)苯基)丙烷、2,2-双(4-((甲基)丙烯酰氧基十一乙氧基)苯基)丙烷、2,2-双(4-((甲基)丙烯酰氧基十二乙氧基)苯基)丙烷、2,2-双(4-((甲基)丙烯酰氧基十三乙氧基)苯基)丙烷、2,2-双(4-((甲基)丙烯酰氧基十四乙氧基)苯基)丙烷、2,2-双(4-((甲基)丙烯酰 氧基十五乙氧基)苯基)丙烷、2,2-双(4-((甲基)丙烯酰氧基十六乙氧基)苯基)丙烷等。单个2,2-双(4-((甲基)丙烯酰氧基多乙氧基)苯基)丙烷分子内的氧化乙烯基数优选为4-20，更优选为8-15。这些化合物可以单独使用，也可以两种以上组合使用。Examples of the bisphenol A (meth)acrylate compound 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. Examples of the 2,2-bis(4-((meth)acryloyloxypolyethoxy)phenyl)propane 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)acryloyloxy nonaethoxy)phenyl ) Propane, 2,2-bis(4-((meth)acryloyloxydecethoxy)phenyl)propane, 2,2-bis(4-((meth)acryloyloxyundecyl Oxy)phenyl)propane, 2,2-bis(4-((meth)acryloyloxydodecyloxy)phenyl)propane, 2,2-bis(4-((meth)propene Acyloxytridecethoxy)phenyl)propane, 2,2-bis(4-((meth)acryloyloxytetradecyloxy)phenyl)propane, 2,2-bis(4- ((Meth)acryloyloxy pentaethoxy)phenyl)propane, 2,2-bis(4-((meth)acryloyloxyhexadecyloxy)phenyl)propane, etc. 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.
作为上述分子内具有氨酯键的(甲基)丙烯酸酯化合物，示例性地可以列举出如：在β位具有OH基的(甲基)丙烯酸类单体和二异氰酸酯化合物(如，异佛尔酮二异氰酸酯、2,6-甲苯二异氰酸酯、2,4-甲苯二异氰酸酯、1,6-六亚甲基二异氰酸酯等)的加成反应产物、三((甲基)丙烯酰氧基四亚乙基二醇异氰酸酯)六亚甲基异氰脲酸酯、EO改性氨酯二(甲基)丙烯酸酯、PO改性氨酯二(甲基)丙烯酸酯、EO,PO改性氨酯二(甲基)丙烯酸酯。这些化合物可以单独使用，也可两种以上组合使用。Examples of the (meth)acrylate compound having a urethane bond in the molecule include (meth)acrylic monomers having an OH group at the β 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.
作为上述壬基苯氧基多乙烯氧基丙烯酸酯，示例性地可以列举出如：壬基苯氧基四乙烯氧基丙烯酸酯、壬基苯氧基五乙烯氧基丙烯酸酯、壬基苯氧基六乙烯氧基丙烯酸酯、壬基苯氧基七乙烯氧基丙烯酸酯、壬基苯氧基八乙烯氧基丙烯酸酯、壬基苯氧基九乙烯氧基丙烯酸酯、壬基苯氧基十乙烯氧基丙烯酸酯、壬基苯氧基十一乙烯氧基丙烯酸酯。这些化合物可以单独使用，也可两种以上组合使用。Examples of the nonylphenoxy polyvinyloxy acrylate 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.
作为上述苯二甲酸类化合物，示例性地可以列举出如：γ-氯-β-羟基丙基-β'-(甲基)丙烯酰氧基乙基邻苯二甲酸酯、β-羟基烷基-β'-(甲基)丙烯酰氧基烷基邻苯二甲酸酯。这些化合物可以单独使用，也可两种以上组合使用。Examples of the above-mentioned phthalic acid compounds include γ-chloro-β-hydroxypropyl-β'-(meth)acryloyloxyethyl phthalate and β-hydroxyalkane. -Β'-(meth)acryloyloxyalkyl phthalate. These compounds may be used alone or in combination of two or more.
作为上述(甲基)丙烯酸烷基酯，示例性地可以列举出如：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸异丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸仲丁酯、(甲基)丙烯酸叔丁酯、(甲基)丙烯 酸2－乙基己酯、(甲基)丙烯酸苯酯、(甲基)丙烯酸异冰片酯、(甲基)丙烯酸羟甲酯、(甲基)丙烯酸羟乙酯、(甲基)丙烯酸羟丙酯、(甲基)丙烯酸-2-羟乙酯、(甲基)丙烯酸-2-羟丙酯、(甲基)丙烯酸苄基酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸四氢糠基酯、(甲基)丙烯酸异辛酯、乙氧基化壬基酚(甲基)丙烯酸酯、丙二醇聚丙烯醚二(甲基)丙烯酸酯、1,9-壬二醇二(甲基)丙烯酸酯、1,10-癸二醇二(甲基)丙烯酸酯、乙氧基化聚四氢呋喃二醇二(甲基)丙烯酸酯、乙氧基化聚丙二醇二(甲基)丙烯酸酯等。其中，优选为(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、三羟甲基丙烷三(甲基)丙烯酸酯、乙氧基化三羟甲基丙烷三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、乙氧化季戊四醇四(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、二季戊四醇六丙烯酸酯。这些化合物可以单独使用，也可两种以上组合使用。Examples of the aforementioned (meth)acrylic acid alkyl esters include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, and (meth)acrylic acid. Propyl ester, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, phenyl (meth)acrylate, Isobornyl (meth)acrylate, hydroxymethyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, (meth Group) 2-hydroxypropyl acrylate, benzyl (meth) acrylate, amyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isooctyl (meth) acrylate, ethoxy Nonylphenol (meth)acrylate, propylene glycol polypropylene ether di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth) Acrylate, ethoxylated polytetrahydrofurandiol di(meth)acrylate, ethoxylated polypropylene glycol di(meth)acrylate, etc. Among them, 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.
从提高分辨率、耐镀覆性、密合性的角度来看，所述具有烯属不饱和双键的化合物优选自双酚A类(甲基)丙烯酸酯化合物和分子内具有氨酯键的(甲基)丙烯酸酯化合物。从提高灵敏度和解析度的角度来看，优选双酚A类(甲基)丙烯酸酯化合物。作为双酚A类(甲基)丙烯酸酯化合物的市售品，示例性地，有2,2-双(4-((甲基)丙烯酰氧基多乙氧基)苯基)丙烷(如新中村化学工业株式会社制，BPE-200)、多乙氧基双酚A甲基丙烯酸酯(如新中村化学工业株式会社制，BPE-5000；日立化成株式会社制，FA-321M)、2,2-双(4-((甲基)丙烯酰氧基多丁氧基)苯基)丙烷(如新中村化学工业株式会社，BPE-1300)等。From the viewpoint of improving resolution, plating resistance, and adhesion, 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. As a commercially available product of a bisphenol A (meth)acrylate compound, there is exemplified 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 , 2-bis(4-((meth)acryloyloxypolybutoxy)phenyl)propane (such as Shin Nakamura Chemical Industry Co., Ltd., BPE-1300), etc.
在100质量份感光性树脂组合物中，具有烯属不饱和双键的化合物的含量优选为20-50质量份，更优选为25-45质量份。当所述具有烯属不饱和双键的化合物的含量在20质量份以上时，感光性树脂组合物的灵敏度和解析度 会进一步提高；当其含量在50质量份以下，感光性树脂组合物更易薄膜化，且对于蚀刻处理的耐久性进一步提高。In 100 parts by mass of the photosensitive resin composition, 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. When the content of the compound having an ethylenically unsaturated double bond is more than 20 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.
其它光引发剂和/或增感剂Other photoinitiators and/or sensitizers
感光性树脂组合物中还含有其它光引发剂或增感剂，以通过协同效应来增加感光树脂体系的相容性、感光度及解析度。所述的其它光引发剂和/或增感剂可以包括(但不限于)双咪唑类、吡唑啉类、芳香族酮类、蒽醌类、苯偶姻和苯偶姻烷基醚类、肟酯类、三嗪类、三苯胺类、香豆素类、噻吨酮类、吖啶类及其它本领域技术人员已知的光引发剂。这些光引发剂可以单独使用或两种以上组合使用。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.
示例性地，双咪唑衍生物可以是2,2',5-三(2-氯苯基)-4-(3,4-二甲氧基苯基)-4',5'-二苯基-二咪唑、2,2',5-三(2-氟苯基)-4-(3,4-二甲氧基苯基)-4',5'-二苯基-二咪唑、2,2'-二(2,4-二氯苯基)-4,4'5,5'-四苯基-二咪唑、2,2'-二(2-氟苯基)-4-(2-氯苯基)-5-(3,4-二甲氧基苯基)-4',5'-二苯基-二咪唑、2,2'-二(2-氟苯基)-4,4',5,5'-四苯基-二咪唑、2,2'-二(2-甲氧基苯基)-4,4',5,5'-四苯基-二咪唑、2,2'-二(2-氯-5-硝基苯基)-4,4'-二(3,4-二甲氧基苯基)-5,5'-二(2-氯苯基)-二咪唑、2,2'-二(2-氯-5-硝基苯基)-4-(3,4-二甲氧基苯基)-5-(2-氯苯基)-4',5'-二苯基-二咪唑、2,2'-二(2,4-二氯苯基)-4,4'-二(3,4-二甲氧基苯基)-5,5'-二(2-氯苯基)-二咪唑、2-(2,4-二氯苯基)-4-(3,4-二甲氧基苯基)-2',5-二(2-氯苯基)-4',5'-二苯基-二咪唑、2-(2,4-二氯苯基)-2'-(2-氯苯基)-4,4'，5,5'-四苯基-二咪唑、2,2'-二(2,4-二氯苯基)-4,4',5,5'-四苯基-二咪唑、及相似物。这些双咪唑衍生物可以单独使用或两种以上组合使用。Illustratively, 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-methoxyphenyl)-4,4',5,5'-tetraphenyl-diimidazole, 2,2 '-Bis(2-chloro-5-nitrophenyl)-4,4'-bis(3,4-dimethoxyphenyl)-5,5'-bis(2-chlorophenyl)-di Imidazole, 2,2'-bis(2-chloro-5-nitrophenyl)-4-(3,4-dimethoxyphenyl)-5-(2-chlorophenyl)-4',5 '-Diphenyl-diimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4'-bis(3,4-dimethoxyphenyl)-5,5'- Bis(2-chlorophenyl)-diimidazole, 2-(2,4-dichlorophenyl)-4-(3,4-dimethoxyphenyl)-2',5-bis(2-chloro Phenyl)-4',5'-diphenyl-diimidazole, 2-(2,4-dichlorophenyl)-2'-(2-chlorophenyl)-4,4', 5,5' -Tetraphenyl-diimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-diimidazole, and the like. These bisimidazole derivatives can be used alone or in combination of two or more.
示例性地，吡唑啉类化合物可以是1-苯基-3-(4-叔丁基苯乙烯基)-5- (4-叔丁基苯基)吡唑啉、1-苯基-3-联苯基-5-(4-叔丁基苯基)吡唑啉、乙氧基化(9)三羟甲基吡唑啉酯、乙氧基化(10)双酚A吡唑啉酯及其相似物。这些吡唑啉类化合物可以单独使用，也可以两种以上组合使用。Exemplarily, 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.
示例性地，芳香族酮类衍生物可以是苯乙酮、2,2-二甲氧基-2-苯基苯乙酮、2,2-二乙氧基-2-苯基苯乙酮、1,1-二氯苯乙酮、二苯甲酮、4-苯甲酰基二苯硫醚、4-苯甲酰基-4'-甲基二苯硫醚、4-苯甲酰基-4'-乙基二苯硫醚、4-苯甲酰基-4'-丙基二苯硫醚、4,4'-双(二乙基氨基)二苯甲酮、4-对甲苯巯基二苯甲酮、2,4,6-三甲基二苯甲酮、4-甲基二苯甲酮、4,4'-双(二甲氨基)二苯甲酮、4,4'-双(甲基、乙基氨基)二苯甲酮、苯乙酮二甲基缩酮、苯偶酰二甲基缩酮、α,α'-二甲基苯偶酰缩酮、α,α-二乙氧基苯乙酮、2-羟基-2-甲基-1-苯基丙酮、1-羟基环己基苯甲酮、2-羟基-2-甲基-1-对羟乙基醚基苯基丙酮、2-甲基1-(4-甲巯基苯基)-2-吗啉1-丙酮、2-苄基-2-二甲氨基-1-(4-吗啉苯基)1-丁酮、苯基双(2,4,6-三甲基苯甲酰基)氧膦、2,4,6-三甲基苯甲酰基-二苯基氧化膦、2-羟基-1-{3-[4-(2-羟基-2-甲基-丙酰基)-苯基]-1,1,3-三甲基-茚-5-基}-2-甲基丙酮、2-羟基-1-{1-[4-(2-羟基-2-甲基-丙酰基)-苯基]-1,3,3-三甲基-茚-5-基}-2-甲基丙酮、1-(4-异丙基苯基)-2-羟基-2-甲基丙-1-酮、4-(2-羟基乙氧基)-苯基-(2-羟基-2-丙基)酮、及相似物。这些芳香族酮类衍生物可以单独使用或两种以上组合使用。Exemplarily, 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, α,α'-dimethyl benzyl ketal, α,α-diethoxy styrene Ketone, 2-hydroxy-2-methyl-1-phenylacetone, 1-hydroxycyclohexyl benzophenone, 2-hydroxy-2-methyl-1-p-hydroxyethyl ether phenylacetone, 2-methyl 1-(4-methylmercaptophenyl)-2-morpholine 1-acetone, 2-benzyl-2-dimethylamino-1-(4-morpholinephenyl) 1-butanone, phenyl bis( 2,4,6-trimethylbenzoyl)phosphine oxide, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 2-hydroxy-1-{3-[4-(2-(2- Hydroxy-2-methyl-propionyl)-phenyl]-1,1,3-trimethyl-inden-5-yl}-2-methylacetone, 2-hydroxy-1-{1-[4- (2-hydroxy-2-methyl-propionyl)-phenyl)-1,3,3-trimethyl-inden-5-yl)-2-methylacetone, 1-(4-isopropylbenzene Group)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)-phenyl-(2-hydroxy-2-propyl)one, and the like. These aromatic ketone derivatives can be used alone or in combination of two or more.
示例性地，蒽醌类衍生物可以是2-苯基蒽醌、2,3-二苯基蒽醌、1-氯蒽醌、2-甲基蒽醌、2,3-二甲基蒽醌、2-乙基蒽-9,10-二乙酯、1,2,3-三甲基蒽-9,10-二辛脂、2-乙基蒽-9,10-二(4-氯丁酸甲酯)、2-(3-((3-乙基氧杂环丁烷-3-基)甲氧基)-3-氧代丙基)蒽-9,10-二乙酯、9,10-二丁氧基蒽、9,10-二乙氧基-2-乙基蒽、9,10-二(3-氯丙氧基)蒽、9,10-二(2-羟基乙巯基) 蒽、9,10-二(3-羟基-1-丙巯基)蒽、及相似物。这些蒽醌类衍生物可以单独使用或两种以上组合使用。Exemplarily, 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-hydroxyethylmercapto) Anthracene, 9,10-bis(3-hydroxy-1-propylmercapto)anthracene, and the like. These anthraquinone derivatives can be used alone or in combination of two or more.
示例性地，苯偶姻和苯偶姻烷基醚类衍生物可以是苯偶姻甲基醚、苯偶姻乙基醚、苯偶姻苯基醚、及相似物。这些苯偶姻和苯偶姻烷基醚类衍生物可以单独使用或两种以上组合使用。Illustratively, 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.
示例性地，肟酯类衍生物可以是1-(4-苯硫基苯基)-正辛烷-1,2-二酮-2-苯甲酸肟酯、1-(6-(2-甲基苯甲酰基)-9-乙基咔唑-3-基)-乙烷-1-酮-乙酸肟酯、1-(6-(2-甲基苯甲酰基)-9-乙基咔唑-3-基)-丁烷-1-酮-乙酸肟酯、1-(6-(2-甲基苯甲酰基)-9-乙基咔唑-3-基)-丙烷-1-酮-乙酸肟酯、1-(6-(2-甲基苯甲酰基)-9-乙基咔唑-3-基)-1-环己基-甲烷-1-酮-乙酸肟酯、1-(6-(2-甲基苯甲酰基)-9-乙基咔唑-3-基)-3-环戊基-丙烷-1-酮-乙酸肟酯、1-(4-苯硫基苯基)-(3-环戊基)-丙烷-1,2-二酮-2-苯甲酸肟酯、1-(4-苯硫基苯基)-(3-环己基)-丙烷-1,2-二酮-2-环己基甲酸肟酯、1-(6-(2-甲基苯甲酰基)-9-乙基咔唑-3-基)-(3-环戊基)-丙烷-1，2-二酮-2-乙酸肟酯、1-(6-邻甲基苯甲酰基-9-乙基咔唑-3-基)-(3-环戊基)-丙烷-1,2-二酮-2-苯甲酸肟酯、1-(4-苯甲酰基二苯硫醚)-(3-环戊基丙酮)-1-肟乙酸酯、1-(6-邻甲基苯甲酰基-9-乙基咔唑-3-基)-(3-环戊基丙酮)-1-肟环己基甲酸酯、1-(4-苯甲酰基二苯硫醚)-(3-环戊基丙酮)-1-肟环己基甲酸酯、1-(6-邻甲基苯甲酰基-9-乙基咔唑-3-基)-(3-环戊基)-丙烷-1,2-二酮-2-邻甲基苯甲酸肟酯、1-(4-苯硫基苯基)-(3-环戊基)-丙烷-1,2-二酮-2-环己基甲酸肟酯、1-(4-噻吩甲酰基-二苯硫醚-4'-基)-3-环戊基-丙烷-1-酮-乙酸肟酯、1-(4-苯甲酰基二苯硫醚)-(3-环戊基)-丙烷-1,2-二酮-2-肟乙酸酯、1-(6-硝基-9-乙基咔唑-3-基)-3-环己基-丙烷-1-酮-乙酸肟酯、1-(6- 邻甲基苯甲酰基-9-乙基咔唑-3-基)-3-环己基-丙烷-1-酮-乙酸肟酯、1-(6-噻吩甲酰基-9-乙基咔唑－3-基)-(3-环己基丙酮)-1-肟乙酸酯、1-(6－呋喃糠甲酰基-9-乙基咔唑－3-基)-(3-环戊基丙酮)-1-肟乙酸酯、1,4-二苯基丙烷-1,3-二酮-2-乙酸肟酯、1-(6-糠酰基-9-乙基咔唑-3-基)-(3-环己基)-丙烷-1,2-二酮-2-乙酸肟酯、1-(4-苯硫基苯基)-(3-环已基)-丙烷-1,2-二酮-2-乙酸肟酯、1-(6-呋喃糠甲酰基-9-乙基咔唑-3-基)-(3-环己基丙酮)-1-肟乙酸酯、1-(4-苯硫基苯基)-(3-环已基)-丙烷-1,2-二酮-3-苯甲酸肟酯、1-(6-噻吩甲酰基-9-乙基咔唑-3-基)-(3-环己基)-丙烷-1,2-二酮-2-乙酸肟酯、2-((苯甲酰氧基)亚氨基)-1-苯基丙烷-1-酮、1-苯基-1,2-丙二酮-2-(氧代乙酰基)肟、1-(4-苯硫基苯基)-2-(2-甲基苯基)-乙烷-1,2-二酮-2-乙酸肟酯、1-(9,9-二丁基-7-硝基芴-2-基)-3-环己基-丙烷-1-酮-乙酸肟酯、1-(4-(4-(噻吩-2-甲酰基)苯硫基)苯基)-3-环戊基丙烷-1,2-二酮-2-乙酸肟酯、1-(9,9-二丁基-2-基)-3-环己基丙基丙烷-1,2-二酮-2-乙酸肟酯、1-(6-(2-(苯甲酰氧基亚氨基)-3-环己基丙基-9-乙基咔唑-3-基)辛烷-1,2-二酮-2-苯甲酸肟酯、1-(7-硝基-9,9-二烯丙基芴-2-基)-1-(2-甲基苯基)甲酮-乙酸肟酯、1-(6-(2-甲基苯甲酰基)-9-乙基咔唑-3-基)-3-环戊基-丙烷-1-酮-苯甲酸肟酯、1-(7-(2-甲基苯甲酰基)-9,9-二丁基芴-2-基)-3-环己基丙烷-1,2-二酮-2-乙酸肟酯、1-(6-(呋喃-2-甲酰基)-9-乙基咔唑-3-基)-3-环己基丙烷-1,2-二酮-2-乙氧甲酰肟酯、及相似物。这些肟酯类衍生物可以单独使用或两种以上组合使用。Exemplarily, 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-cyclopentyl-propane-1-one-oxime acetate, 1-(4-phenylthiophenyl) -(3-cyclopentyl)-propane-1,2-dione-2-benzoic acid oxime ester, 1-(4-phenylthiophenyl)-(3-cyclohexyl)-propane-1,2- Dione-2-cyclohexylcarboxylic acid oxime ester, 1-(6-(2-methylbenzoyl)-9-ethylcarbazol-3-yl)-(3-cyclopentyl)-propane-1, 2-dione-2-acetoxime, 1-(6-o-methylbenzoyl-9-ethylcarbazol-3-yl)-(3-cyclopentyl)-propane-1,2-di Keto-2-benzoic acid oxime ester, 1-(4-benzoyldiphenyl sulfide)-(3-cyclopentylacetone)-1-oxime acetate, 1-(6-o-methylbenzoyl -9-ethylcarbazol-3-yl)-(3-cyclopentylacetone)-1-oxime cyclohexyl formate, 1-(4-benzoyldiphenyl sulfide)-(3-cyclopentane Acetone)-1-oxime cyclohexyl formate, 1-(6-o-methylbenzoyl-9-ethylcarbazol-3-yl)-(3-cyclopentyl)-propane-1,2 -Diketone-2-o-toluic acid oxime ester, 1-(4-phenylthiophenyl)-(3-cyclopentyl)-propane-1,2-diketo-2-cyclohexylcarboxylic acid oxime ester , 1-(4-thienyl-diphenyl sulfide-4'-yl)-3-cyclopentyl-propane-1-one-oxime acetate, 1-(4-benzoyl diphenyl sulfide) -(3-cyclopentyl)-propane-1,2-dione-2-oxime acetate, 1-(6-nitro-9-ethylcarbazol-3-yl)-3-cyclohexyl- Propane-1-one-oxime acetate, 1-(6-o-toluoyl-9-ethylcarbazol-3-yl)-3-cyclohexyl-propane-1-one-oxime acetate, 1 -(6-thiophenoyl-9-ethylcarbazol-3-yl)-(3-cyclohexylacetone)-1-oxime acetate, 1-(6-furanfuranoyl-9-ethylcarbamate Oxazol-3-yl)-(3-cyclopentylacetone)-1-oxime acetate, 1,4-diphenylpropane-1,3-dione-2-acetoxime, 1-(6- Furoyl-9-ethylcarbazol-3-yl)-(3-cyclohexyl)-propane-1,2-dione-2-acetic acid oxime ester, 1-(4-phenylthiophenyl)-( 3-cyclohexyl)-propane-1,2-dione-2-acetoxime, 1-(6- Furanfuranoyl-9-ethylcarbazol-3-yl)-(3-cyclohexylacetone)-1-oxime acetate, 1-(4-phenylthiophenyl)-(3-cyclohexyl )-Propane-1,2-dione-3-benzoic acid oxime ester, 1-(6-thienyl-9-ethylcarbazol-3-yl)-(3-cyclohexyl)-propane-1, 2-dione-2-acetoxime ester, 2-((benzoyloxy)imino)-1-phenylpropane-1-one, 1-phenyl-1,2-propanedione-2- (Oxoacetyl)oxime, 1-(4-phenylthiophenyl)-2-(2-methylphenyl)-ethane-1,2-dione-2-acetic acid oxime ester, 1-( 9,9-dibutyl-7-nitrofluoren-2-yl)-3-cyclohexyl-propane-1-one-oxime acetate, 1-(4-(4-(thiophen-2-formyl) Phenylthio)phenyl)-3-cyclopentylpropane-1,2-dione-2-acetic acid oxime ester, 1-(9,9-dibutyl-2-yl)-3-cyclohexylpropyl Propane-1,2-dione-2-acetoxime, 1-(6-(2-(benzoyloxyimino)-3-cyclohexylpropyl-9-ethylcarbazol-3-yl ) Octane-1,2-dione-2-benzoic acid oxime ester, 1-(7-nitro-9,9-diallylfluoren-2-yl)-1-(2-methylphenyl ) Methanone-oxime acetate, 1-(6-(2-methylbenzoyl)-9-ethylcarbazol-3-yl)-3-cyclopentyl-propane-1-one-benzoic acid oxime Ester, 1-(7-(2-methylbenzoyl)-9,9-dibutylfluoren-2-yl)-3-cyclohexylpropane-1,2-dione-2-acetic acid oxime ester, 1-(6-(furan-2-formyl)-9-ethylcarbazol-3-yl)-3-cyclohexylpropane-1,2-dione-2-ethoxyformyl oxime ester, and the like Thing. These oxime ester derivatives can be used alone or in combination of two or more.
示例性地，三嗪衍生物可以是2-(4-乙基联苯)-4,6-双(三氯甲基)-1,3,5-三嗪、2-(3,4-亚甲氧基苯基)-4,6-双(三氯甲基)-1,3,5-三嗪、3-{4-[2,4-双(三氯甲基)-s-三嗪-6-基]苯硫基}丙酸、1,1,1,3,3,3-六氟异丙基-3-{4-[2,4-双(三氯甲 基)-s-三嗪-6-基]苯硫基}丙酸酯、乙基-2-{4-[2,4-双(三氯甲基)-s-三嗪-6-基]苯硫基}乙酸酯、2-乙氧基乙基-2-{4-[2,4-双(三氯甲基)-s-三嗪-6-基]苯硫基}乙酸酯、环己基-2-{4-[2,4-双(三氯甲基)-s-三嗪-6-基]苯硫基}乙酸酯、芐基-2-{4-[2,4-双(三氯甲基)-s-三嗪-6-基]苯硫基}乙酸酯、3-{氯-4-[2,4-双(三氯甲基)-s-三嗪-6-基]苯硫基}丙酸、3-{4-[2,4-双(三氯甲基)-s-三嗪-6-基]苯硫基}丙醯胺、2,4-双(三氯甲基)-6-p-甲氧基苯乙烯基-s-三嗪、2,4-双(三氯甲基)-6-(1-p-二甲基胺基苯基)-1,3,-丁二烯基-s-三嗪、2-三氯甲基-4-胺基-6-p-甲氧基苯乙烯基-s-三嗪、及相似物。这些三嗪衍生物可以单独使用或两种以上组合使用。Exemplarily, 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]phenylthio}acetate, cyclohexyl-2 -{4-[2,4-bis(trichloromethyl)-s-triazin-6-yl]phenylthio}acetate, benzyl-2-{4-[2,4-bis(tri Chloromethyl)-s-triazin-6-yl]phenylthio}acetate, 3-{chloro-4-[2,4-bis(trichloromethyl)-s-triazin-6-yl ]Phenylthio}propionic acid, 3-{4-[2,4-bis(trichloromethyl)-s-triazin-6-yl]phenylthio}propionamide, 2,4-bis(tris Chloromethyl)-6-p-methoxystyryl-s-triazine, 2,4-bis(trichloromethyl)-6-(1-p-dimethylaminophenyl)-1 ,3,-butadienyl-s-triazine, 2-trichloromethyl-4-amino-6-p-methoxystyryl-s-triazine, and the like. These triazine derivatives can be used alone or in combination of two or more.
示例性地，三苯胺类化合物可以是N,N-双-[4-(2-苯乙烯基-1-基)-苯基]-N,N-双(2-乙基-6甲基苯基)-1,1-双苯基-4,4-二胺、N,N-双-[4-(2-苯乙烯基-1-基)-4′-甲基苯基]-N,N-双(2-乙基-6甲基苯基)-1,1-双苯基-4,4-二胺及其相似物。这些三苯胺类化合物可以单独使用，也可以两种以上组合使用。Exemplarily, 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.
示例性地，香豆素衍生物可以是3,3'-羰基双(7-二乙胺香豆素)、3-苯甲酰基-7-二乙胺香豆素、3,3'-羰基双(7-甲氧基香豆素)、7-(二乙氨基)-4-甲基香豆素、3-(2-苯并噻唑)-7-(二乙基胺基)香豆素、7-(二乙氨基)-4-甲基-2H-1-苯并吡喃-2-酮(7-(二乙氨基)-4-甲基香豆素)、3-苯甲酰基-7-甲氧基香豆素、及相似物。这些香豆素衍生物可以单独使用或两种以上组合使用。Exemplarily, 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.
示例性地，噻吨酮类衍生物可以是噻吨酮、2,4-二甲基噻吨酮、2,4-二乙基噻吨酮、2,4-二异丙基噻吨酮、2-氯噻吨酮、1-氯-4-丙氧基噻吨酮、异丙基噻吨酮、二异丙基噻吨酮、及相似物。这些噻吨酮类衍生物可以单独使用或两种以上组合使用。Exemplarily, 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.
示例性地，吖啶类衍生物可以是9-苯基吖啶、9-对甲基苯基吖啶、9-间甲基苯基吖啶、9-邻氯苯基吖啶、9-邻氟苯基吖啶、2-乙基-2-(羟甲基)-1,3-丙二醇醚环乙烷醚的[4-(9-吖啶基)苯氧基]乙酸酯、1,7-二(9-吖啶基)庚烷、9-乙基吖啶、9-(4-溴苯基)吖啶、9-(3-氯苯基)吖啶、1,7-双(9-吖啶)庚烷、1,5-双(9-吖啶戊烷)、1,3-双(9-吖啶)丙烷、及相似物。这些吖啶类衍生物可以单独使用或两种以上组合使用。Exemplarily, 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 be used alone or in combination of two or more.
优选地，在100质量份感光性树脂组合物中，所述其它光引发剂或增感剂的含量为不超过8质量份。Preferably, in 100 parts by mass of the photosensitive resin composition, the content of the other photoinitiator or sensitizer is not more than 8 parts by mass.
助剂Additives
除了上述各组分，任选地，本发明的感光性树脂组合物中还可以根据需要包含适量的其它助剂。示例性地，助剂可以为孔雀绿等染料、三溴苯基砜、无色结晶紫等光显色剂、颜料、填充剂、增塑剂、稳定剂、涂布助剂、剥离促进剂等。In addition to the above-mentioned components, the photosensitive resin composition of the present invention may optionally contain an appropriate amount of other auxiliary agents as needed. Illustratively, 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. .
作为上述染料、颜料及光显色剂，示例性地，可以是：三(4-二甲基氨基苯基)甲烷、三(4-二甲基氨基-2甲基苯基)甲烷、荧烷染料、甲苯磺酸一水合物、碱性品红、酞菁绿及酞菁蓝等酞菁系、金胺碱、副品红、结晶紫、甲基橙、尼罗蓝2B、维多利亚蓝、孔雀绿、金刚绿、碱性蓝20、艳绿、伊红、乙基紫、赤藓红钠盐B、甲基绿、苯酚酞、茜素红S、百里香酚酞、甲基紫2B、喹那定红、玫瑰红钠琼脂、米塔尼尔黄、百里香酚磺酞、二甲苯酚蓝、甲基橘、橘IV、二苯基流卡巴腙、2,7-二氯荧光素、泛甲基红、刚果红、本佐红紫4B、α-萘基红、非那西汀、甲基紫、维多利亚纯蓝BOH、罗丹明6G、二苯基胺、二苄基苯胺、三苯基胺、二乙基苯胺、二苯基-对伸苯基二胺、对甲苯胺、苯并三氮唑、甲基苯丙***、4,4’-联苯基二胺、邻氯 苯胺、白色结晶紫、白色孔雀绿、白色苯胺、白色甲基紫、偶氮系等有机颜料、二氧化钛等无机颜料。在具有良好对比度的考量下，优选使用三(4-二甲基氨基苯基)甲烷(即，隐色结晶紫，LCV)。这些染料、颜料及光显色剂可以单独一种使用，也可两种以上混合使用。As the above-mentioned 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 Flucarbazone, 2,7-Dichlorofluorescein, Pan-Methyl Red , Congo red, Benzo red purple 4B, α-naphthyl red, phenacetin, methyl violet, Victoria blue BOH, rhodamine 6G, diphenylamine, dibenzylaniline, triphenylamine Ethylaniline, diphenyl-p-phenylene diamine, p-toluidine, benzotriazole, methamphetamine, 4,4'-biphenyldiamine, o-chloroaniline, white crystal violet , White malachite green, white aniline, white methyl violet, azo and other organic pigments, titanium dioxide and other inorganic pigments. In consideration of having a good contrast, it is preferable to use 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.
作为上述填充剂，示例性地，可以是：二氧化硅、氧化铝、滑石、碳酸钙、硫酸钡等填充剂(不包含上述无机颜料)。填充剂可以单独一种使用，也可两种以上混合使用。As the filler, for example, 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.
作为上述增塑剂，示例性地，可以是：邻苯二甲酸二丁酯、邻苯二甲酸二庚酯、邻苯二甲酸二辛酯、邻苯二甲酸二烯丙酯等邻苯二甲酸酯、三甘醇二乙酸酯、四乙二醇二乙酸酯等乙二醇酯、对甲苯磺酰胺、苯磺酰胺、正丁基苯磺酰胺等磺酰胺类、磷酸三苯酯、三甲基磷酸酯、三乙基磷酸酯、三苯基磷酸酯、三甲苯基磷酸酯、三二甲苯基磷酸酯、甲苯基二苯基磷酸酯、三二甲苯基磷酸酯、2-萘基二苯基磷酸酯、甲苯基二2,6-二甲苯基磷酸酯、芳香族缩合磷酸酯、三(氯丙基)磷酸酯、三(三溴新戊基)磷酸酯、含卤缩合磷酸酯、二辛酸三甘醇酯，二(2-乙基己酸)三甘醇酯、二庚酸四甘醇酯、癸二酸二乙酯、辛二酸二丁酯、磷酸三(2-乙基乙酯)、Brij 30〔C 12H 25(OCH 2CH 2) 4OH〕、和Brij 35〔C 12H 25(OCH 2CH 2) 20OH〕等。增塑剂可以单独一种使用，也可两种以上混合使用。 As the above-mentioned 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(chloropropyl) phosphate, tri(tribromo neopentyl) phosphate, halogen-containing condensed phosphate , Triethylene glycol dicaprylate, triethylene glycol bis(2-ethylhexanoate), tetraethylene glycol diheptanoate, diethyl sebacate, dibutyl suberate, tris(2-ethyl phosphate Ethyl ester), Brij 30 [C 12 H 25 (OCH 2 CH 2 ) 4 OH], Brij 35 [C 12 H 25 (OCH 2 CH 2 ) 20 OH], etc. The plasticizer may be used alone or in combination of two or more.
作为上述稳定剂，示例性地，可以是：氢醌、1,4,4-三甲基-重氮二环(3.2.2)-壬-2-烯-2,3-二氧化物、1-苯基-3-吡唑烷酮、对甲氧基苯酚、烷基和芳基取代的氢醌和醌、叔丁基邻苯二酚、1,2,3-苯三酚、树脂酸铜、萘胺、β-萘酚、氯化亚铜、2,6-二叔丁基对甲酚、吩噻嗪、吡啶、硝基苯、二硝基苯、对甲苯醌和氯醌等。稳定剂可以单独一种使用，也可两种以上混合使 用。As 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, β-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.
作为上述涂布助剂，从安全性、通用性方面考虑，可以是：丙酮、甲醇、甲基醇、乙基醇、异丙基醇、甲基乙基酮、丙二醇单甲基醚乙酸酯、乳酸乙酯、环己酮、γ-丁内酯、二氯甲烷等。涂布助剂可以单独一种使用，也可两种以上混合使用。As 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, γ-butyrolactone, dichloromethane, etc. The coating aid may be used alone or in combination of two or more.
作为上述剥离促进剂，示例性地，可以是：苯磺酸、甲苯磺酸、二甲苯磺酸、苯酚磺酸，甲基、丙基、庚基、辛基、癸基、十二烷基等烷基苯磺酸等。剥离促进剂可以单独一种使用，也可两种以上混合使用。As the above 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.
优选地，在100质量份感光性树脂组合物中，助剂含量为不超过10质量份。Preferably, in 100 parts by mass of the photosensitive resin composition, the content of the auxiliary agent is not more than 10 parts by mass.
<应用><application>
本发明的感光性树脂组合物可以制备成干膜，即感光性树脂层叠体，并应用于印刷电路板、保护图案、导体图案、引框线、半导体封装的制造中，经过不同的工序在不同的基材上形成所需要的图案。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.
本发明的感光性树脂组合物也可以通过湿膜涂布机涂布至各对应制造步骤中对应的基材上，即作为湿膜应用于印刷电路板、保护图案、导体图案、引框线、半导体封装的制造中，经过不同的工序在不同的基材上形成所需要的图案。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.
干膜应用Dry film applications
本发明的干膜即感光性树脂层叠体，其包含：感光性树脂组合物形成的感光性树脂层以及支撑该感光性树脂层的支撑体。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.
通常，干膜的制作包括：将感光性树脂组合物涂布在支撑体上，干燥以形成感光性树脂层；任选地，根据需要贴合覆盖膜(保护层)。较佳地， 干燥条件是60-100℃下干燥0.5-15min。感光性树脂层的厚度优选为5-95μm，再优选为10-50μm，更优选为15-30μm。若感光性树脂层的厚度小于5μm，则绝缘性不佳，而若感光性树脂层的厚度超过95μm，则解析度可能会较差。Generally, 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. Preferably, the drying condition is at 60-100°C for 0.5-15 min. The thickness of the photosensitive resin layer is preferably 5-95 μm, more preferably 10-50 μm, and more preferably 15-30 μm. If the thickness of the photosensitive resin layer is less than 5 μm, the insulation is not good, and if the thickness of the photosensitive resin layer exceeds 95 μm, the resolution may be poor.
作为支撑体，具体实例可以是各种类型的塑胶膜，如聚对苯二甲酸乙二醇酯、聚乙烯萘二酸酯、聚丙烯、聚乙烯、纤维素乙酸酯、聚甲基丙烯酸烷酯、甲基丙烯酸酯共聚物、聚氯乙烯、聚乙烯醇、聚碳酸酯、聚苯乙烯、玻璃纸、氯乙烯共聚物、聚酰胺、聚亚酰胺、乙烯氯-乙酸乙烯酯共聚物、聚四氟乙烯、聚三氟乙烯及其相似物。此外，亦可使用由两种或以上材料所组成的复合材料。优选地，使用的是具有极佳光穿透性的聚对苯二甲酸乙二醇酯。支撑体的厚度优选为5-150μm，更优选为10-50μm。As a support, specific examples may be various types of 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. In addition, composite materials composed of two or more materials can also be used. Preferably, polyethylene terephthalate having excellent light penetration is used. The thickness of the support is preferably 5-150 μm, and more preferably 10-50 μm.
对感光性树脂组合物的涂布并无特殊限制，例如可使用喷涂法、滚筒式涂布法、旋转式涂布法、狭缝式涂布法、压缩涂布法、帘涂法、染料涂布法、线条涂布法、刮刀涂布法、辊涂法、刮涂法、喷涂法、浸涂法等常规方法。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.
进一步地，本发明提供上述干膜在制造印刷电路板中的应用，包括：Further, the present invention provides the application of the above dry film in the manufacture of printed circuit boards, including:
(1)层叠工序：将感光性树脂层叠体层叠于覆铜层叠板或柔性基板上；(1) Lamination step: Laminating a photosensitive resin laminate on a copper-clad laminate or flexible substrate;
(2)曝光工序：对感光性树脂层叠体中的感光性树脂层进行曝光，以图像状照射活性光线使曝光部分进行光固化；(2) 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;
(3)显影工序：将感光性树脂层的未曝光部分用显影液去除，以形成保护图案；(3) Development process: remove the unexposed part of the photosensitive resin layer with a developing solution to form a protective pattern;
(4)导体图案形成工序：对覆铜层叠板或柔性基板表面的未被保护图案覆盖的部分进行刻蚀或镀覆；(4) 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;
(5)剥离工序：将保护图案从该覆铜层叠板或柔性基板剥离。(5) Peeling step: peeling the protective pattern from the copper-clad laminate or flexible substrate.
进一步地，本发明提供上述干膜在制造保护图案中的应用，包括如上所述的层叠工序、曝光工序和显影工序，不同在于：层叠工序中感光性树脂层叠体可层叠于各种不同材质的基板上。Further, 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.
进一步地，本发明提供上述干膜在制造导体图案中的应用，包括如上所述的层叠工序、曝光工序、显影工序和导体图案形成工序，不同在于：层叠工序中感光性树脂层叠体层叠于金属板或金属覆膜绝缘板上。Further, 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.
进一步地，本发明提供上述干膜在制造引框线中的应用，包括如上所述的层叠工序、曝光工序、显影工序、和导体图案形成工序，不同在于：层叠工序中感光性树脂层叠体层叠于金属板上，导体图案形成工序中对未被保护图案覆盖的部分进行刻蚀。Further, 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.
进一步地，本发明提供上述干膜在制造半导体封装中的应用，包括如上所述的层叠工序、曝光工序、显影工序、和导体图案形成工序，不同在于：层叠工序中感光性树脂层叠体层叠于具有大规模集成电路的晶片上，导体图案形成工序中对未被保护图案覆盖的部分进行镀覆。Further, 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.
湿膜应用Wet film applications
本发明的感光性树脂组合物可以湿膜方式直接涂布在基板上使用，以用于印刷电路板、保护图案、导体图案、引框线、半导体封装等的制造。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.
非限制性地，可利用辊涂、刮涂、喷涂、浸涂等常规方法将感光性树脂组合物涂布于基板上，干燥后形成感光性树脂层。Without limitation, 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.
在基板上形成感光性树脂层后，后续工序如曝光工序、显影工序、导体图案形成工序和剥离工序，均可参照干膜应用的方式进行。After the photosensitive resin layer is formed on the substrate, subsequent processes such as an exposure process, a development process, a conductor pattern forming process, and a peeling process can all be performed with reference to the application method of the dry film.
工序步骤Process steps
曝光工序中，曝光可以列举出掩模曝光法(布线图的负或正掩模图形将 活性光线呈图像状地照射的方法)、投影曝光法，也可以采用通过激光直接成像曝光法、数字光学处理曝光法等直接描画曝光法将活性光线呈图像状地照射的方法。作为活性光线的光源，可使用公知的光源，如碳弧灯、汞蒸气弧灯、超高压示灯、高压示灯、氙灯、氩气激光等气体激光、YAG激光等固体激光、半导体激光和氮化镓系蓝紫色激光等有效放射出紫外线的光源。此外，还可以使用照相用泛光灯、日光灯等有效放射出可见光的光源。In the exposure process, 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 The method of direct drawing exposure, such as the processing exposure method, irradiates the active light in the form of an image. As the light source of active light, 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. In addition, a light source that efficiently emits visible light such as a floodlight for photography or a fluorescent lamp can also be used.
本发明的感光性树脂组合物对活性光线的光源种类没有特别限制，曝光量优选为10-1000mJ/cm 2。 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 .
显影工序中，将感光性树脂层的未曝光部分用显影液去除。在感光性树脂层上存在支撑体的情况下，可利用自动剥离器等先除去支撑体，然后再使用碱性水溶液、水系显影液、有机溶剂等显影液除去未曝光部分。碱性水溶液的例子可以是0.1-5质量％的碳酸钠溶液、0.1-5质量％的碳酸钾溶液、0.1-5质量％的氢氧化钠溶液等，pH值优选为9-11。碱性水溶液中还可以加入表面活性剂、消泡剂、有机溶剂等。显影的方式可以是浸渍、喷雾、刷洗等常规方式。In the development step, the unexposed portion of the photosensitive resin layer is removed with a developer. 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. Examples of 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.
刻蚀处理中，以形成于基板上的抗蚀图案(即保护图案)作为掩模，将未被覆盖的电路形成用基板的导体层刻蚀除去，从而形成导体图案。刻蚀处理的方法可以根据待去除的导体层而选择。例如，作为蚀刻液可以列举出氧化铜溶液、氧化铁溶液、碱蚀刻溶液、过氧化氢系蚀刻液等。In the etching process, using the resist pattern (ie, the protection pattern) formed on the substrate as a mask, 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. For example, examples of the etching solution include copper oxide solution, iron oxide solution, alkali etching solution, hydrogen peroxide-based etching solution, and the like.
镀敷处理中，以形成于基板上的抗蚀图案为掩模，在未被覆盖的电路形成用基板的绝缘板上镀覆铜和焊锡等。镀敷处理后，除去抗蚀图案从而形成导体图案。作为镀敷处理的方法，既可以是电镀处理，也可以是无电 解镀覆处理，优选无电解镀覆处理。作为无电解镀覆处理，可以列举出：硫酸铜镀敷和焦磷酸铜镀敷等铜镀敷、高均匀焊锡(high-throw solder)镀敷等焊锡镀敷、瓦特浴(硫酸镍-氯化镍)镀敷和氨基磺酸镍镀敷等镍镀敷、硬质金镀敷和软质金镀敷等金镀敷。In the 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. As a method of 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.
抗蚀图案的除去可以通过比显影工序中使用的碱性水溶液碱性更强的水溶液来进行剥离。作为强碱性水溶液的实例，可使用例如1-10质量％的氢氧化钠水溶液。The resist pattern can be removed by an aqueous solution that is more alkaline than the alkaline aqueous solution used in the development step. As an example of a strong alkaline aqueous solution, for example, a 1-10% by mass sodium hydroxide aqueous solution can be used.
附图说明BRIEF DESCRIPTION
图1是对比产物1的高效液相色谱图。Figure 1 is a high performance liquid chromatogram of Comparative Product 1.
图2是BCIM中两种连接位化合物的结构示意图。Figure 2 is a schematic diagram of the structure of two linking compounds in BCIM.
图3是对比产物2的高效液相色谱图。Figure 3 is a high performance liquid chromatogram of Comparative Product 2.
图4是对比产物3的高效液相色谱图。4 is a high performance liquid chromatogram of Comparative Product 3.
图5是产物1的高效液相色谱图。Figure 5 is a high performance liquid chromatogram of product 1.
图6是产物2的高效液相色谱图。Figure 6 is a high performance liquid chromatogram of product 2.
图7是产物1-2和对比产物1-3的感光度测试结果对比。Figure 7 is a comparison of the sensitivity test results of product 1-2 and comparative product 1-3.
具体实施方式detailed description
以下将结合具体实施例对本发明作进一步详细说明，但不应将其理解为对本发明保护范围的限制。The present invention will be further described in detail in conjunction with specific embodiments below, but it should not be construed as limiting the protection scope of the present invention.
一、2,2'-二(邻氯苯基)-4,4',5,5'-四苯基二咪唑混合光引发剂1. 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyldiimidazole mixed photoinitiator
1.制备实施例1. Preparation Example
(1)对比产物1的制备(1) Preparation of Comparative Product 1
向1L的四口烧瓶中投入79g 2-(2-氯苯基)-4,5-二苯基咪唑、1.2g醋酸、0.5g四丁基溴化铵和300g甲苯，加热搅拌，在60-65℃时滴加163g次氯酸钠(11％的次氯酸钠水溶液)，滴加结束后保温反应，反应过程中取样通过HPLC进行中控，直至2-(2-氯苯基)-4,5-二苯基咪唑反应完全，结束保温。保温反应结束后，用40g纯水洗涤四次，再用20g甲苯萃取一次水层，然后将上述萃取得到的有机层加热至约65℃时过滤，再将过滤后的有机层进行减压蒸馏至产品完全析出，再加入纯水50g，搅拌、降温、抽干、烘料得75g对比产物1。79g 2-(2-chlorophenyl)-4,5-diphenylimidazole, 1.2g acetic acid, 0.5g tetrabutylammonium bromide and 300g toluene were put into a 1L four-necked flask, heated and stirred at 60- At 65°C, 163 g of sodium hypochlorite (11% aqueous solution of sodium hypochlorite) was added dropwise, and the reaction was kept warm after the dropwise addition. During the reaction, a sample was taken and controlled by HPLC until 2-(2-chlorophenyl)-4,5-diphenyl The imidazole reaction is complete and the heat preservation is ended. After the end of the holding reaction, wash it with 40 g of pure water four times, and then extract the aqueous layer once with 20 g of toluene, then filter the organic layer obtained by the above extraction to about 65° C. and then distill the filtered organic layer under reduced pressure to The product completely precipitated, and then added 50g of pure water, stirred, cooled, dried and baked to obtain 75g of Comparative Product 1.
使用高效液相色谱仪和单晶衍射对对比产物1进行检测。图1是对比产物1的高效液相色谱图，显示对比产物1的主成分占总量的82.52％。 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.
尽管产物1的主成分在液相中只有一个峰，但是对分离得到的单一的主成分进行单晶衍射分析，单晶衍射显示有两个峰形。结合结构特征可以确定，两个单咪唑偶合其主要产物是其中一个咪唑上的含有氢的N与另一个咪唑上2位的C连接而成的混合物，图2所示结构为单晶衍射得到的立体结构，结构显示为本发明中所述的1-2’和2’-3两种连接位。Although 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.
对比产物1的主成分为1-2’和3-2’两种连接位的化合物，结构式如下所示，分别为：The product of Comparative Product 1 is composed of two compounds with 1-2' and 3-2' linking sites. The structural formulas are as follows:
(Ⅰ)：2,2’-二(邻氯苯基)-4,4’,5,5’-四苯基-1,2’-二咪唑，和(Ⅰ): 2,2’-bis(o-chlorophenyl)-4,4’,5,5’-tetraphenyl-1,2’-diimidazole, and
(II)：2,2’-二(邻氯苯基)-4,4’,5,5’-四苯基-2’,3-二咪唑；(II): 2,2’-bis(o-chlorophenyl)-4,4’,5,5’-tetraphenyl-2’,3-diimidazole;
Figure PCTCN2019120523-appb-000003
Figure PCTCN2019120523-appb-000003
进行LCMS进一步确认结构。质谱分析借助仪器附带软件得到659与660分子碎片峰，产品的分子量为658，与T+1和T+2吻合。Perform LCMS to further confirm the structure. The mass spectrometry analysis obtained the 659 and 660 molecular fragment peaks with the software attached to the instrument. The molecular weight of the product was 658, which was in agreement with T+1 and T+2.
(2)对比产物2的制备(2) Preparation of Comparative Product 2
参照上述对比产物1的制备，不同之处在于在得到对比产物1之后进行打浆处理，所用打浆液为甲苯和水的混合溶液，甲苯和水的比例为1:4，打浆液和产物1的重量比为1:1，打浆后离心、抽滤、烘干得到产物2。Refer to the preparation of the above comparative product 1, 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. After beating, the product 2 is obtained by centrifugation, suction filtration and drying.
使用高效液相色谱仪对对比产物2进行检测。结果显示，对比产物2的主要成分(由式(Ⅰ)和式(II)所示结构的化合物)占对比产物2总量的86.18％(见图3)。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).
(3)对比产物3的制备(3) Preparation of Comparative Product 3
参照上述对比产物2的制备，不同之处在于所用打浆液为甲醇，打浆液和产物1的重量比为1:1，打浆后离心、抽滤、烘干得到对比产物3。Referring to the preparation of the above comparative product 2, 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.
检测结果显示，对比产物3的主要成分(由式(Ⅰ)和式(II)所示结构的化合物)占对比产物3总量的92.10％(见图4)。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).
(4)产物1的制备(4) Preparation of product 1
参照上述对比产物1的制备，不同之处在于在得到对比产物1之后进行重结晶处理(升温回流搅拌后再降温析晶)，所用重结晶溶液为甲苯， 重结晶溶液和产物1的重量比为1.2:1，降温后离心、淋洗、烘干得到产物1。Referring to the preparation of the above comparative product 1, 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.
检测结果显示，产物1的主要成分(由式(Ⅰ)和式(II)所示结构的化合物)占产物1总量的97.45％(见图5)。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).
(5)产物2的制备(5) Preparation of product 2
参照上述产物1的制备，不同之处在于所用重结晶溶液为甲苯和甲醇的混合溶剂，甲苯和甲醇的比例为1:1，重结晶溶液和产物1的重量比为1.2:1，降温后离心、抽滤、烘干得到产物5。Referring to the preparation of the above product 1, the difference is that 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.
检测结果显示，产物2的主要成分(由式(Ⅰ)和式(II)所示结构的化合物)占产物2总量的99.27％(见图6)。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).
(6)产物3的制备(6) Preparation of product 3
参照上述产物1的制备，不同之处在于所用相转移催化剂为18-冠醚-6，最终得到产物3。Referring to the preparation of the above product 1, the difference is that the phase transfer catalyst used is 18-crown-6, and finally the product 3 is obtained.
检测结果显示，产物3的主要成分(由式(Ⅰ)和式(II)所示结构的化合物)占产物3总量的97.23％。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.
(7)对比产物4的制备(7) Preparation of Comparative Product 4
参照上述对比产物1的制备，不同之处在于未添加醋酸，最终得到对比产物4。Referring to the preparation of the above comparative product 1, the difference is that no acetic acid is added, and finally a comparative product 4 is obtained.
检测结果显示，对比产物4的主要成分(由式(Ⅰ)和式(II)所示结构的化合物)占对比产物4总量的93.30％。The test results show that the main components of the comparative product 4 (compounds of the structure represented by formula (I) and formula (II)) account for 93.30% of the total of the comparative product 4.
(8)产物4的制备(8) Preparation of product 4
参照上述对比产物4的制备，不同之处在于在得到对比产物4之后进行打浆处理，所用打浆液为甲苯和甲醇的混合溶液，甲苯和甲醇的比例为 1:1，打浆液和产物1的重量比为0.6:1，打浆后离心、抽滤、烘干得到产物4。Refer to the preparation of the above Comparative Product 4 except that the comparison product 4 is subjected to beating treatment. 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. After beating, the product 4 is obtained by centrifugation, suction filtration and drying.
检测结果显示，产物4的主要成分(由式(Ⅰ)和式(II)所示结构的化合物)占产物4总量的98.67％。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.
(9)产物5的制备(9) Preparation of product 5
向1L的四口烧瓶中投入79g 2-(2-氯苯基)-4,5-二苯基咪唑、1.3g片碱、0.5g四丁基溴化铵和300g甲苯，加热搅拌，在60-65℃时滴加156g次氯酸钠(11％的次氯酸钠水溶液)，滴加结束后保温反应，反应过程中取样通过HPLC进行中控，直至2-(2-氯苯基)-4,5-二苯基咪唑反应完全，结束保温。保温反应结束后，用40g纯水洗涤四次，再用20g甲苯萃取一次水层，然后将上述萃取得到的有机层加热至约65℃时过滤，再将过滤后的有机层进行减压蒸馏至有产品析出，降温、抽干、烘料得69g产物5。Into a 1L four-necked flask, put 79g of 2-(2-chlorophenyl)-4,5-diphenylimidazole, 1.3g of caustic soda, 0.5g of tetrabutylammonium bromide and 300g of toluene, heat and stir at 60 -65g sodium hypochlorite (11% aqueous solution of sodium hypochlorite) was added dropwise at -65°C, and the reaction was kept warm after the dropwise addition. During the reaction, samples were taken and controlled by HPLC until 2-(2-chlorophenyl)-4,5-diphenyl The reaction of the imidazole is complete, and the heat preservation is ended. After the end of the holding reaction, wash it with 40 g of pure water four times, and then extract the aqueous layer once with 20 g of toluene, then filter the organic layer obtained by the above extraction to about 65° C. and then distill the filtered organic layer under reduced pressure to There was product precipitation, cooling, drying and baking to obtain 69g of product 5.
检测结果显示，产物5的主要成分(由式(Ⅰ)和式(II)所示结构的化合物)占产物5总量的99.41％。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.
2.感光度测试2. Sensitivity test
根据表1中所示配方，将各组分混合均匀制得实施例1-2以及比较例1-3的感光性树脂组合物，以测试感光度。表中各组分用量单位均为g。According to the formulations shown in Table 1, 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.
表1Table 1
Figure PCTCN2019120523-appb-000004
Figure PCTCN2019120523-appb-000004
Figure PCTCN2019120523-appb-000005
Figure PCTCN2019120523-appb-000005
表1中，TMPTA购自天津市北联精细化学品开发有限公司，NPG购自深圳市鹏顺兴科技有限公司，PGMEA购自济南汇丰达化工有限公司。In Table 1, TMPTA was purchased from Tianjin Beilian Fine Chemical Development Co., Ltd., NPG was purchased from Shenzhen Pengshunxing Technology Co., Ltd., and PGMEA was purchased from Jinan Huifengda Chemical Co., Ltd.
按上述配方进行样品配制，混合均匀后取1.0mg样品平铺于坩埚底部，后放入差示扫描量热仪(型号：DSC8000，厂家：PerkinElmer)的炉体中进行测试。Prepare the sample according to the above formula. After mixing, take 1.0 mg of the sample and lay it flat on the bottom of the crucible, and then put it into the furnace body of the differential scanning calorimeter (model: DSC8000, manufacturer: PerkinElmer) for testing.
峰值代表最大放热量，mw/mg，放热量越大，感光度越高。The peak value represents the maximum heat dissipation, mw/mg, the greater the heat dissipation, the higher the sensitivity.
斜率代表固化速率，斜率越小感光度越高。The slope represents the curing rate, the smaller the slope, the higher the sensitivity.
如图7所示，感光度测试结果为：对比产物1＜对比产物2＜对比产物3＜产物1＜产物2。该结果表明，BCIM混合光引发剂应用后表现出的感光度与其中式(Ⅰ)和式(Ⅱ)两种化合物的含量密切相关。随着两者在BCIM中的占比逐步提升，整体感光度相应提高，特别是当含量高于97％时，BCIM的放热量达到12mw/mg，可以满足干膜对曝光时间的要求。As shown in FIG. 7, 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.
光引发剂的感光度决定了干膜的曝光时间，而曝光时间是影响干膜图像非常重要的因素，曝光不足，抗蚀膜聚合不够，显影时胶膜溶胀、***，线条不清晰，色泽暗淡，甚至脱胶；曝光过度，将产生显影困难、胶膜发脆、余胶等问题。因此，本发明的BCIM混合光引发剂中式(Ⅰ)和式(Ⅱ)化合物的总含量优选在97％以上，更优选99％以上。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. Underexposure, insufficient polymerization of the resist film, swelling and softening of the film during development, unclear lines, color Dim, even degumming; overexposure will cause problems such as difficulty in developing, brittle film, and excess glue. Therefore, 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.
二、感光性树脂组合物2. Photosensitive resin composition
1.制备1. Preparation
1.1碱可溶性聚合物C1的制备1.1 Preparation of alkali soluble polymer C1
在氮气氛围下，向配有搅拌器、回流冷却器、温度计和滴液漏斗的烧瓶中加入由甲基溶纤剂和甲苯以质量比3:2配制而成的混合溶剂500g，搅拌加热至80℃。将甲基丙烯酸100g、甲基丙烯酸乙酯200g、丙烯酸乙酯100g、苯乙烯100g和偶氮双异丁腈0.8g混合制得溶液，随后慢慢滴加至烧瓶中，滴加时间为4小时，滴加结束后继续反应2小时。接着，向烧瓶内滴加溶解有1.2g偶氮双异丁腈的混合溶剂(组成同上)100g，滴加时间为10分钟，滴加结束后，在80℃下进一步反应3小时，再升温至90℃继续反应2小时。反应结束后，过滤得到碱可溶性聚合物C1，重均分子量约为80000。Under a nitrogen atmosphere, to a flask equipped with a stirrer, a reflux cooler, a thermometer, and a dropping funnel, add 500 g of a mixed solvent prepared with methyl cellosolve and toluene in a mass ratio of 3:2, and stir to heat to 80 ℃. A solution was prepared by mixing 100g of methacrylic acid, 200g of ethyl methacrylate, 100g of ethyl acrylate, 100g of styrene, and 0.8g of azobisisobutyronitrile, which was then slowly added dropwise to the flask for 4 hours After the dropwise addition, the reaction was continued for 2 hours. Next, 100 g of a mixed solvent (the composition is the same as above) in which 1.2 g of azobisisobutyronitrile was dissolved was dropped into the flask, and the dropping time was 10 minutes. After the dropwise addition, the reaction was further performed at 80° C. for 3 hours, and the temperature was raised to The reaction was continued at 90°C for 2 hours. After the reaction, the alkali soluble polymer C1 was obtained by filtration, and the weight average molecular weight was about 80,000.
1.2感光性树脂组合物的制备1.2 Preparation of photosensitive resin composition
参照表2中所示配方，将各组分混合均匀制得感光性树脂组合物。如无特别说明，表2中所示份数均为质量份。Referring to the formula shown in Table 2, the components are mixed uniformly to prepare a photosensitive resin composition. Unless otherwise specified, the parts shown in Table 2 are all parts by mass.
表2Table 2
Figure PCTCN2019120523-appb-000006
Figure PCTCN2019120523-appb-000006
Figure PCTCN2019120523-appb-000007
Figure PCTCN2019120523-appb-000007
表2中各组分代号表示的含义如表3中所示。The meaning of each component code in Table 2 is shown in Table 3.
表3table 3
Figure PCTCN2019120523-appb-000008
Figure PCTCN2019120523-appb-000008
Figure PCTCN2019120523-appb-000009
Figure PCTCN2019120523-appb-000009
Figure PCTCN2019120523-appb-000010
Figure PCTCN2019120523-appb-000010
2.性能评价2. Performance evaluation
2.1评价方式2.1 Evaluation method
以干膜应用方式为例，检测上述实施例和比较例所示的感光性树脂组合物的各项应用性能。Taking the dry film application method as an example, each application performance of the photosensitive resin compositions shown in the above examples and comparative examples was tested.
<干膜的制作><Production of dry film>
将感光性树脂组合物充分搅拌，使用棒涂器将其均匀涂布在作为支撑体的25μm厚的聚对苯二甲酸乙二醇酯薄膜的表面上，在干燥机中95℃干燥5分钟，形成厚度为40μm的感光性树脂层，然后在感光性树脂层的没有层压聚对苯二甲酸乙二醇酯薄膜的表面贴合作为保护层的15μm厚的聚乙烯薄膜，获得干膜。The photosensitive resin composition was sufficiently stirred, and it was evenly coated on the surface of a 25 μm 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 μm was formed, and then a 15 μm-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.
<基板表面整平><Plane surface leveling>
作为基板，使用层压有35μm厚的轧制铜箔的1.2mm厚的覆铜层压板，对表面进行湿式抛光辊研磨(3M公司制造的Scotch-Brite(注册商标)HD#600，通过两次)。As a substrate, a 1.2-mm-thick copper-clad laminate laminated with a 35-μm-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 ).
<层压><lamination>
将聚乙烯薄膜保护层从干膜上剥离，然后使用热辊层压机(旭化成(株)制造的AL-70)，以105℃的辊温度将其层压于预热至60℃的覆铜层压板上。气体压力为0.35MPa，层压速度为1.5m/min。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.
<曝光><exposure>
将掩膜放置在作为支撑体的聚对苯二甲酸乙二醇酯薄膜上，通过超高 压汞灯(ORCMANUFACTURINGCO.，LTD.制造的HMW-201KB)进行曝光。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.).
<显影><Development>
剥离聚对苯二甲酸乙二醇酯薄膜，使用碱显影机(FujiKikoCo.，Ltd.制造的干膜用显影机)，将30℃的1质量％的Na 2CO 3水溶液喷雾在感光性树脂层上，用2倍于最小显影时间的时间溶解除去感光性树脂层的未曝光部分。以未曝光部分的感光性树脂层完全溶解所需的最短时间为最小显影时间。 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.
2.2评价内容2.2 Evaluation content
(1)相容性(1) Compatibility
将感光性树脂组合物充分搅拌，使用棒涂布器将组合物均匀涂布于作为支撑体的25μm厚的聚对苯二甲酸乙二醇酯薄膜的表面上。在干燥机中95℃干燥5min，形成感光性树脂层。随后目测感光性树脂层表面，按以下方式分级：The photosensitive resin composition was sufficiently stirred, and the composition was uniformly coated on the surface of a 25 μm-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:
◇：表面均匀；◇: Even surface;
◆：表面析出未溶物。◆: Undissolved matter is deposited on the surface.
(2)感光度(2) Sensitivity
使用具有从透明到黑色的21级明亮度变化的Stouffer制造的21级阶段式曝光表对感光性树脂层曝光15min，以评价其感光度。曝光后，以最小显影时间的2倍时间进行显影，根据抗蚀膜完全残留的阶段式曝光表级数为8的曝光量，进行如下分级：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:
○：曝光量为20mJ/cm 2以下； ○: The exposure is 20mJ/cm 2 or less;
◎：曝光量为20mJ/cm 2-50mJ/cm 2，不包括端值； ◎: The exposure is 20mJ/cm 2 -50mJ/cm 2 , excluding the end value;
●：曝光量为50mJ/cm 2以上。 ●: The exposure is 50mJ/cm 2 or more.
(3)分辨率(3) Resolution
利用具有Line/Space＝10:10-150:150(单位:μm)的布线图案的光掩模进行曝光显影后，测量干膜的分辨率。分辨率是在曝光后显影形成的抗蚀图案中，未曝光部分被清除干净后的图案的最小值。After exposure and development using a photomask having a wiring pattern of Line/Space=10:10-150:150 (unit: μm), 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.
○：分辨率值在30μm以下；○: Resolution value is below 30μm;
◎：分辨率值在30μm-50μm，不包括端值；◎: The resolution value is 30μm-50μm, excluding the end value;
●：分辨率值在50μm以上。●: The resolution value is above 50μm.
(4)亲水性(4) Hydrophilicity
通过感光性树脂层溶解后的沉淀量来评价亲水性。The hydrophilicity was evaluated by the amount of precipitation after the photosensitive resin layer was dissolved.
将感光性树脂组合物充分搅拌，使用棒涂布器均匀地涂布于作为支撑体的25μm厚的聚对苯二甲酸乙二醇酯薄膜的表面上。在干燥机中95℃干燥4min，形成感光性树脂层，层厚约为30.5μm，层重约为3.2g。The photosensitive resin composition was sufficiently stirred, and applied uniformly on the surface of a 25 μm-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 μm and a layer weight of approximately 3.2 g.
将20g碳酸钠溶于2L水中，加1.5ml的P1uronic RPG3110(BASF，Mt.Olive，NJ，此试剂是聚氧乙烯和聚氧丙烯共聚物增塑剂)，制得显影液。将上述附有感光性树脂层的薄膜放入100g显影液中，试样静置直至树脂层溶解，沉淀量按下列等级确定：Dissolve 20g of sodium carbonate in 2L of water, add 1.5ml of P1uronic RPG3110 (BASF, Mt. Olive, NJ, this reagent is polyoxyethylene and polyoxypropylene copolymer plasticizer) to prepare a developer. Put the above-mentioned film with photosensitive resin layer into 100g developer solution, let the sample stand until the resin layer is dissolved, and the amount of precipitation is determined according to the following grade:
0＝沉淀量低于0.005g；0=precipitation amount is less than 0.005g;
1＝少量的细分散浅黄物，沉淀量在0.005-0.01g之间；1 = A small amount of finely dispersed light yellow matter with a precipitation amount between 0.005-0.01g;
5＝中等量浅黄物(通常较细)，沉淀量在0.05-0.08g之间；5=Medium amount of light yellow substance (usually fine), the amount of precipitation is between 0.05-0.08g;
10＝有大量固体层浅黄物(通常呈薄片状)，沉淀量在0.1g以上。10=There are a large number of light yellow substances in the solid layer (usually in the form of flakes), and the amount of precipitation is above 0.1 g.
(5)显影性(5) developability
显影之后通过扫描电子显微镜(SEM)观察光刻胶图案，以评价显影性。After development, the photoresist pattern was observed by a scanning electron microscope (SEM) to evaluate developability.
显影性根据以下标准评价：The developability is evaluated according to the following criteria:
□：在未曝光部分未观察到残留物；□: No residue was observed in the unexposed part;
△：在未曝光部分观察到少量残留物，但残留量可以接受；△: A small amount of residue was observed in the unexposed part, but the amount of residue was acceptable;
×：在未曝光部分观察到明显残留物。×: A clear residue was observed in the unexposed part.
2.3评价结果2.3 Evaluation results
评价结果如表4中所示。The evaluation results are shown in Table 4.
表4Table 4
Figure PCTCN2019120523-appb-000011
Figure PCTCN2019120523-appb-000011
本发明的BCIM混合光引发剂，应用于感光性树脂组合物时具有优异的相容性，组合物的感光度高，分辨率、亲水性和显影性好。相较于比较例4-6的感光性树脂组合物，本发明在感光度、分辨率和亲水性方面性能有明显提升。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.
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上 述实施例的限制，其它的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited by the above embodiments. Any other changes, modifications, substitutions, combinations, changes, modifications, substitutions, combinations, etc. that do not depart from the spirit and principles of the present invention The simplifications should all be equivalent replacement methods, which are all included in the protection scope of the present invention.

Claims (14)

  1. 一种2,2'-二(邻氯苯基)-4,4',5,5'-四苯基二咪唑混合光引发剂，含有具有1-2’连接位的式(I)化合物和具有2’-3连接位的式(II)化合物，且两种化合物的含量之和占该混合光引发剂总量的97％以上，A 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyldiimidazole mixed photoinitiator, containing 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 total amount of the mixed photoinitiator,
    Figure PCTCN2019120523-appb-100001
    Figure PCTCN2019120523-appb-100001
  2. 根据权利要求1所述的2,2'-二(邻氯苯基)-4,4',5,5'-四苯基二咪唑混合光引发剂，其特征在于：式(Ⅰ)和(Ⅱ)两种化合物的含量之和占该混合光引发剂的99％以上。The 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyldiimidazole mixed photoinitiator according to claim 1, characterized in that: formula (I) and ( Ⅱ) The sum of the two compounds accounts for more than 99% of the mixed photoinitiator.
  3. 感光性树脂组合物，包含权利要求1或2所述的2,2'-二(邻氯苯基)-4,4',5,5'-四苯基二咪唑混合光引发剂。A photosensitive resin composition comprising the 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyldiimidazole mixed photoinitiator according to claim 1 or 2.
  4. 根据权利要求3所述的感光性树脂组合物，还包含：碱可溶性聚合物，具有烯属不饱和双键的化合物，其它光引发剂和/或增感剂，以及任选的助剂。The photosensitive resin composition according to claim 3, further comprising: an alkali-soluble polymer, a compound having an ethylenically unsaturated double bond, other photoinitiators and/or sensitizers, and optional auxiliary agents.
  5. 根据权利要求4所述的感光性树脂组合物，其特征在于：所述碱可溶性聚合物选自(甲基)丙烯酸系聚合物、苯乙烯系聚合物、环氧系聚合物、脂肪族聚氨酯(甲基)丙烯酸酯聚合物、芳香族聚氨酯(甲基)丙烯酸酯聚合物、酰胺系树脂、酰胺环氧系树脂、醇酸系树脂、以及酚醛系树脂。The photosensitive resin composition according to claim 4, wherein the alkali-soluble polymer is selected from (meth)acrylic polymers, styrene polymers, epoxy polymers, and aliphatic polyurethanes ( Methacrylate resin, aromatic urethane (meth)acrylate polymer, amide resin, amide epoxy resin, alkyd resin, and phenol resin.
  6. 根据权利要求4或5所述的感光性树脂组合物，其特征在于：所述碱可溶性聚合物是含羧基的碱可溶性聚合物。The photosensitive resin composition according to claim 4 or 5, wherein the alkali-soluble polymer is a carboxyl group-containing alkali-soluble polymer.
  7. 根据权利要求6所述的感光性树脂组合物，其特征在于：所述含羧基的碱可溶性聚合物是由(甲基)丙烯酸酯、乙烯性不饱和羧酸和其他可共聚单体共聚而成的(甲基)丙烯酸酯系聚合物。The photosensitive resin composition according to claim 6, wherein the carboxyl group-containing alkali-soluble polymer is formed by copolymerizing (meth)acrylate, ethylenically unsaturated carboxylic acid and other copolymerizable monomers (Meth)acrylate polymer.
  8. 根据权利要求4所述的感光性树脂组合物，其特征在于：所述具有烯属不饱和双键的化合物是在分子内具有至少一个乙烯性不饱和键的光聚合性化合物。The photosensitive resin composition according to claim 4, wherein the compound having an ethylenically unsaturated double bond is a photopolymerizable compound having at least one ethylenically unsaturated bond in the molecule.
  9. 根据权利要求4或8所述的感光性树脂组合物，其特征在于：所述具有烯属不饱和双键的化合物选自双酚A类(甲基)丙烯酸酯化合物和分子内具有氨酯键的(甲基)丙烯酸酯化合物。The photosensitive resin composition according to claim 4 or 8, wherein the compound having an ethylenically unsaturated double bond is selected from a bisphenol A (meth)acrylate compound and has a urethane bond in the molecule (Meth)acrylate compound.
  10. 根据权利要求4所述的感光性树脂组合物，其特征在于：所述其它光引发剂和/或增感剂选自双咪唑类、吡唑啉类、芳香族酮类、蒽醌类、苯偶姻和苯偶姻烷基醚类、肟酯类、三嗪类、三苯胺类、香豆素类、噻吨酮类、吖啶类光引发剂中的至少一种。The photosensitive resin composition according to claim 4, wherein the other photoinitiator and/or sensitizer is selected from the group consisting of diimidazoles, pyrazolines, aromatic ketones, anthraquinones, and benzene At least one of benzoin and benzoin alkyl ethers, oxime esters, triazines, triphenylamines, coumarins, thioxanthones, and acridine photoinitiators.
  11. 根据权利要求4所述的感光性树脂组合物，其特征在于：所述助剂选自染料、光显色剂、颜料、填充剂、增塑剂、稳定剂、涂布助剂、剥离促进剂中的至少一种。The photosensitive resin composition according to claim 4, wherein the auxiliary agent is selected from the group consisting of dyes, photochromic agents, pigments, fillers, plasticizers, stabilizers, coating aids, and peeling accelerators At least one of them.
  12. 感光性树脂层叠体，包含：权利要求3-11中任一项所述的感光性树脂组合物形成的感光性树脂层，以及支撑该感光性树脂层的支撑体。A photosensitive resin laminate including: the photosensitive resin layer formed of the photosensitive resin composition according to any one of claims 3 to 11; and a support for supporting the photosensitive resin layer.
  13. 权利要求12所述的感光性树脂层叠体在制造印刷电路板、保护图案、导体图案、引框线、半导体封装中的应用。Use of the photosensitive resin laminate according to claim 12 in the manufacture of printed circuit boards, protection patterns, conductor patterns, lead wires, and semiconductor packages.
  14. 权利要求3-11中任一项所述的感光性树脂组合物在制造印刷电路板、保护图案、导体图案、引框线、半导体封装中的应用。Use of the photosensitive resin composition according to any one of claims 3 to 11 in the manufacture of printed circuit boards, protective patterns, conductor patterns, lead wires, and semiconductor packages.
PCT/CN2019/120523 2018-11-30 2019-11-25 Hexaarylbisimidazole hybrid photoinitiator WO2020108420A1 (en)

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