WO2021213087A1 - 乙氧基/丙氧基改性的吡唑啉有机物、其应用、光固化组合物及光刻胶 - Google Patents

乙氧基/丙氧基改性的吡唑啉有机物、其应用、光固化组合物及光刻胶 Download PDF

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WO2021213087A1
WO2021213087A1 PCT/CN2021/081187 CN2021081187W WO2021213087A1 WO 2021213087 A1 WO2021213087 A1 WO 2021213087A1 CN 2021081187 W CN2021081187 W CN 2021081187W WO 2021213087 A1 WO2021213087 A1 WO 2021213087A1
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meth
acrylate
pyrazoline
group
ethoxy
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PCT/CN2021/081187
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English (en)
French (fr)
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钱晓春
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常州强力电子新材料股份有限公司
常州强力先端电子材料有限公司
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Priority to EP21793446.2A priority Critical patent/EP4140983A4/en
Priority to US17/996,773 priority patent/US20230167066A1/en
Priority to JP2022563920A priority patent/JP7465998B2/ja
Publication of WO2021213087A1 publication Critical patent/WO2021213087A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/06—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • 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
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • 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

Definitions

  • the present invention relates to the field of light curing, in particular, to an ethoxy/propoxy modified pyrazoline organic substance, its application, a light curing composition and a photoresist.
  • Ultraviolet curing technology has been widely used due to its fast curing speed and low environmental pollution. Among them, the photoinitiator plays a decisive role in the curing efficiency of the entire curing system. In actual use, some photoinitiators cannot initiate polymerization well due to the limitation of absorption wavelength, and often need to be used in conjunction with sensitizers to improve the initiation efficiency.
  • the sensitizer can continuously transfer the absorbed energy to the photoinitiator, which is equivalent to the catalyst of the photochemical reaction.
  • the application of sensitizers is restricted by many factors, such as solubility and absorption wavelength matching. At this stage, looking for a sensitizer that matches the absorption wavelength of the photoinitiator and has good compatibility has always been a research hotspot in this field.
  • Pyrazoline compounds are a very important class of sensitizers and have been widely used. However, these existing pyrazoline compounds have more or less disadvantages such as unsatisfactory solubility and poor sensitivity improvement effect when used as sensitizers.
  • the dry film development stage usually washes away the unexposed parts with an alkaline aqueous solution, and the pyrazoline compounds will precipitate and adsorb on the surface of the circuit board due to their extremely low solubility, which not only affects the use of dry film, but also It will reduce the precision of the product. Therefore, it is necessary to increase the surface cleaning process of the circuit board in the follow-up, which makes the process cumbersome and greatly increases the cost.
  • the existing literature provides a pyrazoline macromolecular sensitizer, which solves the problems of solubility and formulation compatibility, but in practical applications, it has been found that there are large additions, insufficient sensitivity enhancement, and high viscosity, which are inconvenient to use. problem. Therefore, there is a need for further optimization.
  • the main purpose of the present invention is to provide an ethoxy/propoxy modified pyrazoline organic substance, its application, photocurable composition and photoresist, so as to solve the problem of the existing pyrazoline macromolecular sensitizer There are problems such as large addition amount, insufficient sensitivity improvement, and high viscosity, which is inconvenient to use.
  • an ethoxy/propoxy-modified pyrazoline organic substance is provided.
  • the ethoxy/propoxy-modified pyrazoline organic substance has the formula (I) Structure shown:
  • X and Y each independently represent -CH 2 -CH 2 -or -CH(CH 3 )-CH 2 -; p and q each independently represent an integer of 0-9, and both are not 0 at the same time;
  • R 1 represents a substituent group having a conjugated structure with the pyrazole ring;
  • R 2 represents hydrogen, C 1 ⁇ C 10 linear or branched alkyl, C 4 ⁇ C 10 alkyl cycloalkyl or cycloalkyl alkane Group;
  • R 3 represents hydrogen, a C 1 ⁇ C 20 hydrocarbon group, or a C 6 ⁇ C 20 arylalkyl group.
  • p+q ⁇ 9 preferably, p+q ⁇ 6.
  • R 1 is selected from phenyl, naphthyl, pyrrolyl, imidazolyl, carbazolyl, indolyl, C 2 ⁇ C 10 alkenyl, C 4 ⁇ C 8 cyclodienyl, or, group
  • the hydrogen atoms in each can be independently substituted by the following groups: C 1 ⁇ C 10 linear or branched alkyl, C 4 ⁇ C 10 alkyl cycloalkyl or cycloalkyl alkyl, C 3 ⁇ C 10 cycloalkyl, C 6 ⁇ C 15 aryl, C 6 ⁇ C 12 alkyl aryl, C 6 ⁇ C 12 aryl alkyl, C 2 ⁇ C 20 heteroaryl;
  • R 2 is selected from hydrogen, C 1 ⁇ C 6 linear or branched alkyl;
  • R 3 is selected from hydrogen, C 1 -C 6 linear or branched alkyl, and benzyl.
  • R 1 is selected from phenyl, naphthyl, pyrrolyl, imidazolyl, carbazolyl, indolyl, C 2 ⁇ C 6 alkenyl, C 4 ⁇ C 6 cyclodienyl, C 1 ⁇ C 5 alkyl substituted phenyl, C 3 ⁇ C 6 cycloalkyl substituted by phenyl, C 6 ⁇ C 10 aryl group substituted alkenyl group, C 6 ⁇ C 10 aryl group substituted alkyl group alkenyl group, C 6 ⁇ C 10 arylalkyl substituted alkenyl.
  • R 1 is selected from:
  • R 2 is selected from hydrogen, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl or CH 3 C(CH 2 CH 3 ) 2 -.
  • ethoxy/propoxy modified pyrazoline organics are selected from one or more of the following organics:
  • Another aspect of the present application also provides a photocurable composition, comprising: (A) an alkali-soluble polymer, (B) a compound having an ethylenically unsaturated double bond, (C) a first sensitizer, (D) ) Photoinitiator and/or second sensitizer, (E) other optional auxiliary agents, the first sensitizer includes the above-mentioned ethoxy/propoxy modified pyrazoline organics, and the second sensitizer It is different from the first sensitizer.
  • the alkali-soluble polymer is selected from (meth)acrylic polymers, styrene polymers, epoxy polymers, aliphatic urethane (meth)acrylate polymers, aromatic urethane (meth)acrylic acid One or more of the group consisting of ester polymer, amide resin, amide epoxy resin, alkyd resin, and phenol resin.
  • the compound having an ethylenically unsaturated double bond is selected from compounds obtained by reacting ⁇ , ⁇ -unsaturated carboxylic acids with polyhydric alcohols, bisphenol A (meth)acrylate compounds, ⁇ , ⁇ -unsaturated carboxylic acids A compound obtained by reacting an acid with a glycidyl group-containing compound, a (meth)acrylate compound having a urethane bond in the molecule, nonylphenoxy polyvinyloxy acrylate, ⁇ -chloro- ⁇ -hydroxypropyl - ⁇ '-(meth)acryloyloxyethyl-phthalate, ⁇ -hydroxyethyl- ⁇ '-(meth)acryloyloxyethyl-phthalate, ⁇ -Hydroxypropyl- ⁇ '-(meth)acryloyloxyethyl-phthalate, phthalic acid compounds, one or more of the group consisting of alkyl (meth)acrylate .
  • auxiliary agent is selected from one or more of the group consisting of hydrogen donors, dyes, pigments, light developers, fillers, plasticizers, stabilizers, coating aids and peeling promoters.
  • Another aspect of the present application also provides an application of an ethoxy/propoxy modified pyrazoline organic substance in the field of photocuring.
  • Another aspect of the present application also provides a photoresist, which includes the above-mentioned photocurable composition.
  • the introduction of -CH 2 -CH 2 -O(EO) and/or -CH(CH 3 )-CH 2 -O(PO) makes the above-mentioned EO/PO modified pyrazoline organics It has excellent compatibility with other components in the light-curing system, and is solid, easy to add and use.
  • the absorption band of the structure shown in formula (I) is between 360-400nm, which is particularly suitable as a sensitizer in light curing systems (such as systems containing bisimidazole photoinitiators), which can greatly improve the light curing system.
  • the sensitivity On this basis, the EO/PO-modified pyrazoline organics with the above-mentioned structure have high sensitivity enhancement, small usage amount, solid, and easy to add and use.
  • sludge and "developing garbage” in this application refer to substances accumulated in the developer solution, which are insoluble in the developer solution and will redeposit on the developed substrate, thereby reducing the efficiency of the developer solution.
  • this application provides an ethoxy/propoxy-modified pyrazoline organic compound, and the ethoxy/propoxy-modified pyrazoline organic compound has a structure represented by formula (I) :
  • X and Y each independently represent -CH 2 -CH 2 -or -CH(CH 3 )-CH 2 -; p and q each independently represent an integer of 0-9, and both are not 0 at the same time;
  • R 1 represents a substituent group having a conjugated structure with the pyrazole ring;
  • R 2 represents hydrogen, C 1 ⁇ C 10 linear or branched alkyl, C 4 ⁇ C 10 alkyl cycloalkyl or cycloalkyl alkane Group;
  • R 3 represents hydrogen, a C 1 ⁇ C 20 hydrocarbon group, or a C 6 ⁇ C 20 arylalkyl group.
  • the above-mentioned EO/PO modified pyrazoline organics Due to the introduction of -CH 2 -CH 2 -O(EO) and/or -CH(CH 3 )-CH 2 -O(PO), the above-mentioned EO/PO modified pyrazoline organics have excellent water solubility or water Emulsifying properties, and solid, easy to add and use.
  • the absorption band of the structure shown in formula (I) is between 360-400nm, which is particularly suitable as a sensitizer in light curing systems (such as systems containing bisimidazole photoinitiators), which can greatly improve the light curing system.
  • the sensitivity On this basis, the EO/PO modified pyrazoline organics with the above-mentioned structure have high sensitivity enhancement, small usage amount, and convenient addition and use.
  • p+q ⁇ 9 In consideration of cost, production yield, etc., in a preferred embodiment, p+q ⁇ 9; more preferably, p+q ⁇ 6.
  • R 1 is selected from phenyl, naphthyl, pyrrolyl, imidazolyl, carbazolyl, indolyl, C 2 ⁇ C 10 alkenyl group, C 4 ⁇ C 8 cycloalkenyl group, or, the hydrogen atoms in the group may be independently substituted by the following groups: C 1 ⁇ C 10 linear or branched chain Alkyl group, C 4 ⁇ C 10 alkyl cycloalkyl or cycloalkyl alkyl group, C 3 ⁇ C 10 cycloalkyl group, C 6 ⁇ C 15 aryl group, C 6 ⁇ C 12 alkyl aryl group, C 6 ⁇ C 12 aryl alkyl, C 2 ⁇ C 20 heteroaryl;
  • R 2 is selected from hydrogen, C 1 ⁇ C 6 linear or branched alkyl;
  • R 3 is selected from hydrogen, C 1 -C 6 straight
  • R 1 is selected from phenyl, naphthyl, pyrrolyl, imidazolyl, carbazolyl, Indolyl, C 2 ⁇ C 6 alkenyl, C 4 ⁇ C 6 cyclodienyl, C 1 ⁇ C 5 alkyl substituted phenyl, C 3 ⁇ C 6 cycloalkyl substituted phenyl, C 6 ⁇ C 10 aryl substituted alkenyl, C 6 ⁇ C 10 alkyl aryl substituted alkenyl, C 6 ⁇ C 10 aryl alkyl substituted alkenyl, C 6 ⁇ C 10 aryl alkyl substituted alkenyl.
  • R 1 is selected from one of the following groups:
  • R 2 is selected from hydrogen, methyl, ethyl, propyl, isopropyl, butyl, tertiary Butyl or CH 3 C(CH 2 CH 3 ) 2 -.
  • the ethoxy/propoxy modified pyrazoline organics are selected from one or more of the following organics:
  • the above-mentioned sensitizers Compared with sensitizers of other structures, the above-mentioned sensitizers have the advantages of good light sensitivity, suitable viscosity during use, good adhesion, and low synthesis difficulty.
  • the present invention also provides a preparation method of the EO/PO modified pyrazoline sensitizer represented by formula (I), which comprises the following steps:
  • the sensitizer of the present invention is an improvement and optimization of the existing compound structure.
  • the synthesis involved in the preparation method involves the construction of the pyrazoline ring structure, etherification, etc., which are all conventional processes in the field of organic chemistry.
  • the specific process parameters are easy to determine for those skilled in the art. For example, see the contents described in Chinese Patent CN1515557A and International Patent WO2009/060235A, which are incorporated herein by reference in their entirety.
  • the solvent used is not particularly limited, as long as it is those conventional organic reagents that can dissolve the reaction reagents and do not participate in the reaction, such as dichloromethane, dichloroethane, toluene, benzene, Xylene and so on.
  • the catalyst can be selected from methanesulfonic acid, p-toluenesulfonic acid, and p-toluenesulfonic acid pyridinium salt.
  • the reaction temperature is 0-50°C, and the reaction time is usually 2-10h.
  • the strong base is potassium hydroxide or sodium hydroxide or the like.
  • the reaction is carried out in an organic solvent, and the type of solvent is not particularly limited, and it is generally an alcohol solvent such as methanol and ethanol.
  • the reaction temperature and reaction time vary according to the structure of the raw material c. Generally, the reaction temperature is 0 to 80° C., and the reaction time is usually 2 to 10 h.
  • the reaction is a hydrolysis reaction process.
  • intermediate B can be dissolved in an acid-containing hydrocarbon solvent such as dichloromethane, dichloroethane and the like.
  • the acid can be hydrochloric acid, acetic acid, methanesulfonic acid and the like.
  • the reaction temperature is 0-50°C, and the reaction time is usually 1-10h.
  • the type of solvent used is not particularly limited, as long as it can dissolve the reaction raw materials without adversely affecting the reaction, such as dichloromethane, dichloroethane, acetonitrile, N,N- Dimethylformamide and so on.
  • the acid binding agent can be sodium carbonate, sodium hydroxide, potassium carbonate, sodium methoxide, pyridine, triethylamine and the like.
  • the reaction temperature is 0-100°C, and the reaction time is usually 1-6h.
  • the type of solvent used is not particularly limited, as long as it can dissolve the reaction raw materials without adversely affecting the reaction, such as acetonitrile, N,N-dimethylformamide, N,N -Diethylformamide, etc.
  • the acid binding agent can be sodium carbonate, sodium hydroxide, potassium carbonate, sodium methoxide, pyridine, triethylamine and the like.
  • the reaction temperature is 60-140°C, and the reaction time is usually 4-10h.
  • Another aspect of the present application also provides a photocurable composition, including: (A) alkali-soluble polymer, (B) compound with ethylenically unsaturated double bond, (C) sensitizer, (D) light Initiator, (E) other auxiliary agents, and sensitizers include the sensitizer represented by formula (I).
  • the above-mentioned EO/PO modified pyrazoline sensitizer of the present invention has excellent solubility, and the absorption band is between 360-400nm. It is particularly suitable as a sensitizer in light curing systems, especially systems containing bisimidazole photoinitiators It is used in medium, it has an excellent effect on improving the sensitivity.
  • the EO/PO modified pyrazoline sensitizer of the present invention is applied to a photosensitive resin composition, the composition has the characteristics of good compatibility, high sensitivity, high resolution, high adhesion, and excellent developability , And has good hydrophilicity during development, which can significantly reduce the amount of sludge in the developer during recycling, so that the developer can be used repeatedly and effectively.
  • the EO/PO modified pyrazoline-based sensitizer of the present invention is water-soluble or water-emulsifiable, and this feature eliminates or at least reduces the accumulation of scum and residue in the developer and stripper solution and the uncured photoresist
  • the deposition of scum and residue on equipment and printed circuit boards can improve the yield of printed circuit boards.
  • the alkali-soluble polymer can impart a film-forming function to the photosensitive resin composition.
  • any polymer having such characteristics can be used, and there is no particular limitation.
  • the alkali-soluble polymer is selected from (meth)acrylic polymers, styrene polymers, epoxy polymers, aliphatic polyurethane (meth)acrylate polymers, aromatic One or more of the group consisting of urethane (meth)acrylate polymer, amide resin, amide epoxy resin, alkyd resin, and phenolic resin.
  • the above-mentioned alkali-soluble polymer can be obtained by radical polymerization of polymerizable monomers.
  • polymerizable monomers include but are not limited to: styrene, vinyl toluene, ⁇ -methylstyrene, p-methylstyrene, p-ethylstyrene, p-chlorostyrene, etc.
  • acrylamide derivatives such as acrylamide and diacetone acrylamide
  • ether derivatives of vinyl alcohol such as acrylonitrile and vinyl n-butyl ether
  • (meth)acrylic acid ⁇ -bromo(meth)acrylic acid, ⁇ -chloro(meth)acrylic acid, ⁇ -furyl(meth)acrylic acid, ⁇ -styryl(meth)acrylic acid and other (meth)acrylic acid derivatives
  • alkali-soluble polymers containing carboxyl groups include but are not limited to: Acrylic resin containing (meth)acrylic acid as a monomer unit, which introduces a carboxyl group by using (meth)acrylic acid as a monomer unit; further contains (meth)acrylic acid alkyl ester as a monomer unit in addition to (meth)acrylic acid The copolymer; and in addition to (meth)acrylic acid, further containing (meth)acrylic acid and (meth)acrylic acid alkyl esters other than polymerizable monomers (such as monomers with ethylenically unsaturated groups) as a monomer Body composition copolymer.
  • the alkali-soluble polymer containing a carboxyl group can be obtained by radical polymerization of a polymerizable monomer having a carboxyl group with other polymerizable monomers, especially from (meth)acrylate, ethylene (Meth)acrylic acid ester polymer formed by copolymerization of sexually unsaturated carboxylic acid and other copolymerizable monomers.
  • the above-mentioned (meth)acrylates include, but are not limited to: methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate Ester, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, (methyl) ) Decyl acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, (meth)acrylic acid Diethylaminoethyl, dimethylaminoethyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)
  • ethylenically unsaturated carboxylic acids include, but are not limited to, acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, and itaconic acid, preferably acrylic acid and methacrylic acid. These ethylenically unsaturated carboxylic acids may be used alone or in combination of two or more kinds.
  • the above-mentioned other copolymerizable monomers include, but are not limited to: (meth)acrylamide, n-butyl (meth)acrylate, styrene, vinyl naphthalene, (meth)acrylonitrile, vinyl acetate, vinyl cyclohexane Ethane etc. These other copolymerizable monomers may be used alone or in combination of two or more.
  • the above-mentioned alkali-soluble polymers may be used singly or in combination of two or more kinds.
  • the alkali-soluble polymer used in combination of two or more kinds it can be two or more kinds of alkali-soluble polymers composed of different copolymerization components, two or more kinds of alkali-soluble polymers with different weight average molecular weight, and two or more kinds with different dispersibility.
  • the weight average molecular weight of the alkali-soluble polymer is not particularly limited, and it should be adapted to the specific application environment. Considering the mechanical strength and alkali developability comprehensively, in order to further improve the alkali developability of the alkali soluble polymer and the mechanical strength after film formation, preferably, the weight average molecular weight of the alkali soluble polymer is preferably 15,000 to 200,000, more preferably It is 30,000 to 150,000, particularly preferably 30,000 to 120,000. When the weight average molecular weight is greater than 15,000, the developer resistance after exposure tends to be further improved.
  • 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 to 300 mgKOH/g, more preferably 50 to 250 mgKOH/g, and still more preferably 70 to 250 mg KOH/g, especially Preferably it is 100-250 mgKOH/g.
  • 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, particularly preferably 1.8 to 3.7. When the molecular weight distribution is in the range, the developability is excellent.
  • the content of the alkali-soluble polymer in the composition is preferably 20 to 70 parts by weight, more preferably 30 to 60 parts by weight.
  • the content of the alkali-soluble polymer is more than 20 parts by weight, it can ensure that the photosensitive resin composition has improved durability for plating treatment, etching treatment, etc., and when the content is less than 70 parts by weight, it is beneficial to improve the photosensitive resin composition.
  • the sensitivity is preferably 20 to 70 parts by weight, more preferably 30 to 60 parts by weight.
  • the compound having an ethylenically unsaturated double bond can promote film formation of the photosensitive resin composition.
  • the compound having an ethylenically unsaturated double bond is not particularly limited, as long as a photopolymerizable compound having at least one ethylenically unsaturated bond in the molecule can be used.
  • the compound having an ethylenically unsaturated double bond includes, but is not limited to, the compound obtained by the reaction of ⁇ , ⁇ -unsaturated carboxylic acid and polyol, bisphenol A (meth)acrylate compound, ⁇ , ⁇ - A compound obtained by reacting a saturated carboxylic acid with a glycidyl group-containing compound, a urethane monomer such as a (meth)acrylate compound having a urethane bond in the molecule, nonylphenoxy polyvinyloxy acrylate, ⁇ -chloro- ⁇ -hydroxypropyl- ⁇ '-(meth)acryloyloxyethyl-phthalate, ⁇ -hydroxyethyl- ⁇ '-(meth)acryloyloxyethyl -Phthalates, ⁇ -hydroxypropyl- ⁇ '-(meth)acryloyloxyethyl-phthalate, phthalic acid compounds, and alkyl (meth)acrylate
  • the compound obtained by reacting the above-mentioned ⁇ , ⁇ -unsaturated carboxylic acid with polyol includes but is not limited to: polyethylene glycol di(meth)acrylate with an ethylene number of 2-14 , Polypropylene glycol di(meth)acrylate with a propylene number of 2-14, polyethylene with an ethylene number of 2-14 and a propylene number of 2-14 Polypropylene glycol bis(methyl) )Acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, EO modified trimethylolpropane tri(meth)acrylate, PO modified three Hydroxymethylpropane tri(meth)acrylate, EO, PO modified trimethylolpropane tri(meth)acrylate, tetramethylolmethane tri(meth)acrylate, tetramethylolmethane tetra( Meth) acrylate, dipentaeryth
  • the bisphenol A (meth)acrylate compound includes but is not limited to: 2,2-bis ⁇ 4-[(meth)acryloxypolyethoxy]phenyl ⁇ Propane, 2,2-bis ⁇ 4-[(meth)acryloxypolypropoxy]phenyl ⁇ propane, 2,2-bis ⁇ 4-[(meth)acryloxypolybutoxy Yl]phenyl ⁇ propane, 2,2-bis ⁇ 4-[(meth)acryloxypolyethoxypolypropoxy]phenyl ⁇ propane, etc.
  • the above-mentioned 2,2-bis ⁇ 4-[(meth)acryloyloxypolyethoxy]phenyl ⁇ propane includes but not limited to 2,2-bis ⁇ 4-[(meth)acryloyl Oxydiethoxy]phenyl ⁇ propane, 2,2-bis ⁇ 4-[(meth)acryloxytriethoxy]phenyl ⁇ propane, 2,2-bis ⁇ 4-[( ⁇ Yl)acryloyloxytetraethoxy]phenyl ⁇ propane, 2,2-bis ⁇ 4-[(meth)acryloyloxypentaethoxy]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
  • the number of oxyethylene groups in one molecule of the 2,2-bis ⁇ 4-[(meth)acryloxypolyethoxy]phenyl ⁇ propane is preferably 4-20, more preferably 8- 15. These compounds may be used alone or in combination of two or more kinds.
  • the (meth)acrylate compound having a urethane bond in the molecule includes, but is not limited to, the addition of a (meth)acrylic monomer having an OH group at the ⁇ position and a diisocyanate compound.
  • Reaction product tris[(meth)acryloxytetraethylene glycol isocyanate]hexamethylene isocyanurate, EO modified urethane di(meth)acrylate, PO modified urethane Di(meth)acrylate, EO, PO modified urethane di(meth)acrylate, etc.
  • the diisocyanate compound includes but is not limited to one of isophorone diisocyanate, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate and 1,6-hexamethylene diisocyanate or Many kinds.
  • the aforementioned nonylphenoxy polyvinyloxy acrylate includes, but is not limited to: nonylphenoxy tetravinyloxy acrylate, nonylphenoxy pentavinyloxy acrylate, Nonylphenoxy hexavinyloxy acrylate, nonylphenoxy heptavinyloxy acrylate, nonylphenoxy octavinyloxy acrylate, nonylphenoxy nonavinyloxy acrylate, nonyl One or more of the group consisting of phenoxy decaethyleneoxy acrylate and nonylphenoxy undecethenoxy acrylate.
  • the aforementioned phthalic acid compounds include but are not limited to: ⁇ -chloro- ⁇ -hydroxypropyl- ⁇ '-(meth)acryloyloxyethyl phthalate, One or more of ⁇ -hydroxyalkyl- ⁇ '-(meth)acryloyloxyalkyl phthalate.
  • the above alkyl (meth)acrylate but not limited to methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, (meth)acrylate Isopropyl acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, benzene (meth)acrylate Esters, isobornyl (meth)acrylate, hydroxymethyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, benzyl (meth)acrylate, pentyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isooct
  • the alkyl (meth)acrylate includes, but is not limited to, methyl (meth)acrylate, ethyl (meth)acrylate, trimethylolpropane tri(meth)acrylate, ethoxylated tri
  • methylol propane tri(meth)acrylate pentaerythritol tri(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexaacrylate
  • dipentaerythritol penta(meth)acrylate dipentaerythritol hexaacrylate
  • compounds having ethylenically unsaturated double bonds are selected from A bisphenol A-based (meth)acrylate compound and/or a (meth)acrylate compound having a urethane bond in the molecule.
  • the compound having an ethylenically unsaturated double bond is preferably a bisphenol A (meth)acrylate compound.
  • bisphenol A (meth)acrylate compounds include but are not limited to: 2,2-bis ⁇ 4-[(meth)acryloyloxypolyethoxy]phenyl ⁇ propane (New Nakamura Chemical Kogyo Co., Ltd., BPE-200), 2,2-bis ⁇ 4-[(meth)acryloxypolypropoxy]phenyl)propane (Shin Nakamura Chemical Industry Co., Ltd., BPE-5000; Hitachi Produced by Kasei Co., Ltd., FA-321M), 2,2-bis ⁇ 4-[(meth)acryloxypolybutoxy]phenyl ⁇ propane (Shin Nakamura Chemical Industry Co., Ltd., BPE-1300), etc.
  • the content of the compound (B) having an ethylenically unsaturated double bond is 20-50 parts by weight, more preferably 25-45 parts by weight.
  • the sensitivity and resolution of the photosensitive resin composition will be further improved; when the content is less than 50 parts by weight, the photosensitive resin composition is more easily The film becomes thinner, and the durability against etching treatment is further improved.
  • the first sensitizer (C) is the first sensitizer (C)
  • the first sensitizer (C) is one or more of the EO/PO modified pyrazoline sensitizers, and the structure is as described above.
  • the content of the first sensitizer (C) (EO/PO modified pyrazoline sensitizer) in 100 parts by weight of the photosensitive resin composition is 0.001 to 10 parts by weight, preferably 0.005 to 5 parts by weight. If the content is too small, there is a defect that the photosensitivity is reduced; if the content is too large, there is a defect that the photoresist pattern tends to become wider than the line width of the photomask. Limiting the amount of the sensitizer to the above range is beneficial to improve the photosensitivity and clarity of the photocurable composition.
  • the photosensitive composition may also include a photoinitiator and other types of sensitizers, and the photoinitiators may also be of types commonly used in the art.
  • the aforementioned photoinitiator and/or second sensitizer include, but are not limited to: bisimidazole organics, acridines, aromatic ketones, anthraquinones, benzoin and benzoin alkyl ether organics , One or more of oxime ester organics, triazine organics, coumarin organics, and thioxanthone organics.
  • the bisimidazole compound includes but is not limited to: 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyl-diimidazole, 2, 2',5-Tris(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenyl-1,1'-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-(o-chlorophenyl)-5-( 3,4-Dimethoxyphenyl)-4',5'-diphenyl-d
  • acridine compounds include, but are not limited to: 9-phenylacridine, 9-p-methylphenylacridine, 9-m-methylphenylacridine, 9-o-chlorobenzene Acridine, 9-o-fluorophenylacridine, 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.
  • These acridine compounds can be used alone or in combination of two or more.
  • the aromatic ketone compounds include but are not limited to: acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2 -Phenylacetophenone, 1,1-dichloroacetophenone, benzophenone, 4-benzoyl diphenyl sulfide, 4-benzoyl-4'-methyl diphenyl 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, ethylamino) benzophenone, acetophenone dimethyl ketal,
  • anthraquinone compounds include but are not limited to: 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 2, 3-dimethylanthraquinone, 2-ethylanthracene-9,10-diethyl ester, 1,2,3-trimethylanthracene-9,10-dioctyl ester, 2-ethylanthracene-9,10 -Bis(4-chlorobutyric acid methyl ester), 2- ⁇ 3-[(3-ethyloxetan-3-yl)methoxy]-3-oxopropyl ⁇ anthracene-9,10 -Diethyl, 9,10-dibutoxyanthracene, 9,10-diethoxy-2-ethylanthracene, 9,10-bis(3-chloropropoxy)anthracene, 9,
  • benzoin and benzoin alkyl ether compounds include, but are not limited to: benzoin methyl ether, benzoin ethyl ether, and benzoin phenyl ether. These benzoin and benzoin alkyl ether compounds can be used alone or in combination of two or more.
  • the oxime ester compounds include but are not limited to: 1-(4-phenylthiophenyl)-n-octane-1,2-dione-2-benzoic acid oxime ester, 1- [6-(2-Methylbenzoyl)-9-ethylcarbazol-3-yl]-ethane-1-one-oxime acetate, 1-[6-(2-methylbenzoyl) -9-Ethylcarbazol-3-yl]-butan-1-one-oxime acetate, 1-[6-(2-methylbenzoyl)-9-ethylcarbazol-3-yl] -Propan-1-one-oxime acetate, 1-[6-(2-methylbenzoyl)-9-ethylcarbazol-3-yl]-1-cyclohexyl-methane-1-one-acetic acid Oxime ester, 1-[6-(2-methylbenzoyl)-9-ethylcarbazol-3-yl]-1-
  • triazine compounds include but are not limited to: 2-(4-ethylbiphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(3,4-Methyleneoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 3- ⁇ 4-[2,4-bis(trichloro Methyl)-s-triazin-6-yl]phenylthio)propionic acid, 1,1,1,3,3,3-hexafluoroisopropyl-3- ⁇ 4-[2,4-bis( Trichloromethyl)-s-triazine-6-yl]phenylthio)propionate, ethyl-2- ⁇ 4-[2,4-bis(trichloromethyl)-s-triazine-6 -Yl]phenylthio ⁇ acetate, 2-ethoxyethyl-2- ⁇ 4-[2,4-bis(trichloromethyl)-s-triazin
  • coumarin compounds but not limited to: 3,3'-carbonyl bis(7-diethylamine coumarin), 3-benzoyl-7-diethylamine coumarin , 3,3'-carbonyl bis(7-methoxycoumarin), 7-diethylamino-4-methylcoumarin, 3-(2-benzothiazole)-7-(diethylamine) Base) coumarin, 7-(diethylamino)-4-methyl-2H-1-benzopyran-2-one [7-(diethylamino)-4-methylcoumarin], 3 -Benzoyl-7-methoxycoumarin.
  • These coumarin-based compounds can be used alone or in combination of two or more.
  • thioxanthone compounds include but are not limited to: thioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diethylthioxanthone, Isopropylthioxanthone, 2-chlorothioxanthone, 1-chloro-4-propoxythioxanthone, isopropylthioxanthone, diisopropylthioxanthone.
  • thioxanthone compounds can be used alone or in combination of two or more.
  • coumarin compounds include but are not limited to: 3,3'-carbonyl bis(7-diethylamine coumarin), 3-benzoyl-7-diethylamine coumarin Element, 3,3'-carbonyl bis(7-methoxycoumarin), 7-diethylamino-4-methylcoumarin, 3-(2-benzothiazole)-7-(diethyl Amino) coumarin, 7-(diethylamino)-4-methyl-2H-1-benzopyran-2-one [7-(diethylamino)-4-methylcoumarin], 3-Benzoyl-7-methoxycoumarin.
  • These coumarin-based compounds can be used alone or in combination of two or more.
  • the thioxanthone compound includes: thioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropyl Thioxanthone, 2-chlorothioxanthone, 1-chloro-4-propoxythioxanthone, isopropylthioxanthone, diisopropylthioxanthone.
  • These thioxanthone compounds can be used alone or in combination of two or more.
  • the total content of the other photoinitiator and/or the second sensitizer (D) is 0.01-10 parts by weight.
  • the photosensitive resin composition of the present invention may further contain an appropriate amount of other auxiliary agents as needed.
  • the auxiliary agent includes, but is not limited to, one of hydrogen donors, dyes, pigments, light developers, fillers, plasticizers, stabilizers, coating aids, and peeling promoters. Or multiple.
  • the hydrogen donor is not particularly limited in terms of specific types.
  • the hydrogen donor includes, but is not limited to: amine compounds, carboxylic acid compounds, organosulfur compounds containing mercapto groups, or alcohol compounds. These compounds can be used alone or in combination of two or more of them.
  • hydrogen donors include but are not limited to: triethanolamine, methyl 4-dimethylaminobenzoate, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethyl) Amino) benzophenone, phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenyl Thioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthyloxyacetic acid, 2-mercaptobenzothiazole (MBO), 2-mercaptobenzimidazole (MBI ), dodecyl mercaptan, ethylene glycol bis(3-mercaptobutyrate), etc.
  • MBO 2-mercaptobenzothiazole
  • the dyes, pigments and light developers include but are not limited to: tris(4-dimethylaminophenyl)methane (ie leuco crystal violet, LCV), tris(4-dimethylaminophenyl) Amino-2-methylphenyl) methane, fluoran dyes, toluenesulfonic acid monohydrate, basic fuchsin, phthalocyanine dyes (such as phthalocyanine green and/or phthalocyanine blue), auramine base, by-products Red, Crystal Violet, Methyl Orange, Nile Blue 2B, Victoria Blue, Malachite Green, Diamond Green, Basic Blue 20, Brilliant Green, Eosin, Ethyl Violet, Erythrosine Sodium B, Methyl Green, Benzene Phenolphthalein, Alizarin Red S, Thymolphthalein, Methyl Violet 2B, Quinadine Red, Rose Red Sodium Agar, Mitaniel Yellow, Thymol S
  • the filler includes, but is not limited to, fillers such as silica, alumina, talc, calcium carbonate, and barium sulfate (excluding the above-mentioned inorganic pigments).
  • the filler can be used alone or in a mixture of two or more.
  • the plasticizer includes but is not limited to: phthalate (such as dibutyl phthalate, diheptyl phthalate, dioctyl phthalate, phthalate Diallyl phthalate), sulfonamide organics (such as triethylene glycol diacetate, tetraethylene glycol diacetate and other glycol esters, p-toluenesulfonamide, benzenesulfonamide, n-butylbenzene Sulfonamide), phosphate organics (such as triphenyl phosphate, trimethyl phosphate, triethyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylyl phosphate, tolyl diphenyl Phosphate, trixylyl phosphate, 2-naphthyl diphenyl phosphate, tolyl di 2,6-xylyl phosphate, aromatic condensed phosphate, tris
  • phthalate
  • the stabilizer includes but is not limited to: hydroquinone, 1,4,4-trimethyl-diazobicyclo(3.2.2)-non-2-ene-2,3-di Oxide, 1-phenyl-3-pyrazolidinone, p-methoxyphenol, alkyl and aryl substituted hydroquinone and quinone, tert-butylcatechol, 1,2,3-benzenetriol, resin Copper acid, naphthylamine, ⁇ -naphthol, cuprous chloride, 2,6-di-tert-butyl-p-cresol, phenothiazine, pyridine, nitrobenzene, dinitrobenzene, p-toluoquinone and chloranil, etc. .
  • the stabilizer may be used alone or in combination of two or more kinds.
  • the coating aid includes but is not limited to: 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.
  • the peeling accelerator includes (but is not limited to): benzene sulfonic acid, toluene sulfonic acid, xylene sulfonic acid, phenol sulfonic acid, methyl, propyl, heptyl, octyl, decyl , Dodecyl and other alkyl benzene sulfonic acids.
  • the peeling accelerator may be used alone or in combination of two or more kinds.
  • the content of other additives is 1-10 parts by weight.
  • Another aspect of the application also provides an application of an ethoxy/propoxy modified pyrazoline organic compound of formula (I) in the field of photocuring.
  • the above-mentioned EO/PO modified pyrazoline organics Due to the introduction of -CH 2 -CH 2 -O(EO) and/or -CH(CH 3 )-CH 2 -O(PO), the above-mentioned EO/PO modified pyrazoline organics have excellent water solubility or water Emulsifying properties, and solid, easy to add and use.
  • the absorption band of the structure shown in formula (I) is between 360-400nm, which is particularly suitable as a sensitizer in light curing systems (such as systems containing bisimidazole photoinitiators), which can greatly improve the light curing system.
  • the sensitivity On this basis, the EO/PO modified pyrazoline organics with the above-mentioned structure have high sensitivity enhancement, small usage amount, and convenient addition and use.
  • the photosensitive resin composition of the present invention can be prepared into a dry film, that is, a photosensitive resin laminate, and applied to the manufacture of printed circuit boards, protective patterns, conductor patterns, lead wires, and semiconductor packages. The required pattern is formed on the substrate.
  • the photosensitive resin composition of the present invention can also be directly applied to the corresponding substrate in each corresponding manufacturing step by a wet film coater, that is, applied as a wet film to printed circuit boards, protective patterns, conductor patterns, and lead wires.
  • a wet film coater that is, applied as a wet film to printed circuit boards, protective patterns, conductor patterns, and lead wires.
  • the required patterns are formed on different substrates through different processes.
  • the dry film of the present invention which is a photosensitive resin laminate, includes a photosensitive resin layer formed of a photosensitive resin composition and a support that supports the photosensitive resin layer.
  • the preparation of the dry film includes: coating the photosensitive resin composition on the support and drying to form a photosensitive resin layer; optionally, attaching a cover film (protective layer) as needed.
  • the drying conditions of the above drying step are drying at 60-100° C. for 0.5-15 min.
  • the thickness of the photosensitive resin layer is preferably 5 to 95 ⁇ m.
  • the thickness of the photosensitive resin includes but is not limited to the above range, and limiting it to the above range is beneficial to improve its insulation and resolution. More preferably, the thickness of the photosensitive resin is 10-50 micrometers, More preferably, it is 15-30 micrometers.
  • plastic films such as polyethylene terephthalate, polyethylene naphthalate, polypropylene, polyethylene, cellulose acetate, polymethacrylate Ester, methacrylate copolymer, polyvinyl chloride, polyvinyl alcohol, polycarbonate, polystyrene, cellophane, vinyl chloride copolymer, polyamide, polyimide, vinyl chloride-vinyl acetate copolymer, polytetrafluoroethylene Vinyl fluoride, polytrifluoroethylene.
  • composite materials composed of two or more materials can also be used.
  • polyethylene terephthalate having excellent light transmittance is used.
  • the thickness of the support is preferably 5-150 ⁇ m, more preferably 10-50 ⁇ m.
  • coating method of the photosensitive resin composition There are no particular restrictions on the coating method of the photosensitive resin composition.
  • spray coating, roll coating, spin coating, slit coating, compression coating, curtain coating, and dyes can be used.
  • Conventional methods such as coating method, line coating method, knife coating method, roll coating method, blade coating method, spray coating method, and dip coating method.
  • the present invention provides the application of the above-mentioned dry film in the manufacture of printed circuit boards, including:
  • Laminating step laminating the photosensitive resin laminate on the substrate
  • Exposure step exposing the photosensitive resin layer in the photosensitive resin laminate, irradiating active light in an image form to photocuring the exposed part;
  • Conductor pattern formation process etching or plating the part of the surface of the copper clad laminate or flexible substrate that is not covered by the protective pattern;
  • Peeling step peeling the protective pattern from the copper clad laminate or flexible substrate.
  • the substrate used in the lamination process includes but is not limited to one or more of copper-clad laminates, flexible substrates, metal plates, metal-coated insulating plates, and wafers with large-scale integrated circuits. .
  • the present invention provides the application of the above-mentioned dry film in the manufacture of semiconductor packages.
  • the portion not covered by the protective pattern is etched in the conductor pattern formation process.
  • the portion not covered by the protective pattern is plated in the conductor pattern formation step.
  • the photosensitive resin composition of the present invention can be directly coated on a substrate by a wet film method, and used for the production of printed circuit boards, protective patterns, conductor patterns, lead wires, semiconductor packages, and the like.
  • the photosensitive resin composition may be coated on the substrate by conventional methods such as roll coating, knife coating, spray coating, and dip coating, and dried to form a photosensitive resin layer.
  • the subsequent processes such as the exposure process, the development process, the conductor pattern formation process, and the peeling process can all be performed with reference to the dry film application method.
  • the exposure can include the mask exposure method (a method in which the negative or positive mask pattern of the wiring pattern irradiates the active light in an image form), the projection exposure method, the direct imaging exposure method by laser, and the digital optics.
  • the direct drawing exposure method such as the processing exposure method, is a method in which active light is irradiated in an image form.
  • the light source of active light well-known light sources can be used, such as carbon arc lamp, mercury vapor arc lamp, ultra-high pressure indicator lamp, high pressure indicator lamp, xenon lamp, gas laser such as argon laser, solid laser such as YAG laser, semiconductor laser, and gallium nitride It is a light source that effectively emits ultraviolet rays such as a blue-violet laser. In addition, you can also use a light source that effectively emits visible light, such as a floodlight for photography, a fluorescent lamp, and the like.
  • the photosensitive resin composition of the present invention has no particular limitation on the type of light source of active light, and the exposure amount is preferably 10 to 1000 mJ/cm 2 .
  • the unexposed portion of the photosensitive resin layer is removed with a developer.
  • a developer such as an alkaline aqueous solution, an aqueous developer, an organic solvent, etc.
  • the alkaline aqueous solution includes, but is not limited to, 0.1-5 wt% sodium carbonate solution, 0.1-5 wt% potassium carbonate solution or 0.1-5 wt% sodium hydroxide solution, and the pH value is preferably 9-11. More preferably, the above-mentioned alkaline aqueous solution further includes one or more of surfactants, defoamers or organic solvents. Development methods include but are not limited to conventional methods such as dipping, spraying, and brushing.
  • the resist pattern (ie, protective pattern) formed on the substrate is used as a mask to etch and remove the uncovered conductor layer of the circuit forming substrate, thereby forming a conductor pattern.
  • the etching method can be selected according to the conductor layer to be removed.
  • examples of the etching solution include a copper oxide solution, an iron oxide solution, an alkali etching solution, and a hydrogen peroxide-based etching solution.
  • the plating treatment method includes, but is not limited to, electroplating treatment, or electroless plating treatment, preferably electroless plating treatment.
  • the electroless plating treatment includes but is not limited to: copper plating (copper sulfate plating and/or copper pyrophosphate plating), solder plating (such as high-throw solder plating), Nickel plating (watt bath (nickel sulfate-nickel chloride) plating and/or nickel sulfamate plating), or gold plating (hard gold plating and/or soft gold plating).
  • copper plating copper sulfate plating and/or copper pyrophosphate plating
  • solder plating such as high-throw solder plating
  • Nickel plating watt bath (nickel sulfate-nickel chloride) plating and/or nickel sulfamate plating
  • gold plating hard gold plating and/or soft gold plating.
  • the removal of the resist pattern can be performed 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, 1 to 10% by weight aqueous sodium hydroxide solution can be used.
  • the raw material f namely triethylene glycol monomethyl ether
  • tripropylene glycol monomethyl ether was replaced with tripropylene glycol monomethyl ether to obtain product C2 with a purity of 99.28%.
  • the raw material f namely triethylene glycol monomethyl ether
  • triethylene glycol monobenzyl ether was replaced with triethylene glycol monobenzyl ether to obtain product C3 with a purity of 99.54%.
  • product C4 With reference to the synthesis method of product C1, the raw material a, p-hydroxybenzaldehyde, was replaced with meta-hydroxybenzaldehyde to obtain product C4 with a purity of 99.17%.
  • the raw material c i.e., biacetophenone
  • the raw material c i.e., biacetophenone
  • p-tert-butylbenzaldehyde was replaced with p-tert-butylbenzaldehyde to obtain product C5 with a purity of 99.49%.
  • the raw material c i.e., biacetophenone
  • 1-naphthophenone 1-naphthophenone
  • LCMS was used to confirm the structure of the product C6, and mass spectrometry analysis used the software attached to the instrument to obtain 511 and 512 molecular fragment peaks.
  • the molecular weight of the product was 510, which was consistent with T+1 and T+2.
  • a 1.2mm thick copper clad laminate laminated with 35 ⁇ m thick rolled copper foil was used, and the surface was subjected to wet buffing roll polishing [Scotch-Brite (registered trademark) HD#600 manufactured by 3M Company, passed twice ].
  • the protective layer of the polyethylene film was peeled from the dry film, and then laminated on a copper clad laminate preheated to 60°C at a roll temperature of 105°C using a hot roll laminator (AL-70 manufactured by Asahi Kasei) .
  • the gas pressure is 0.35MPa, and the lamination speed is 1.5m/min.
  • the mask is placed on the polyethylene terephthalate film as a support, and the photosensitive layer is exposed by an ultra-high pressure mercury lamp (HMW-201KB manufactured by ORCMANUFACTURINGCO., LTD.) with an irradiation energy of 60mJ/cm 2 .
  • an ultra-high pressure mercury lamp HMW-201KB manufactured by ORCMANUFACTURINGCO., LTD.
  • the polyethylene terephthalate film was peeled off, and an alkali developing machine (developing machine for dry film manufactured by FujiKiko Co., Ltd.) was used to spray a 1% by mass Na 2 CO 3 aqueous solution at 30°C on the photosensitive resin layer
  • an alkali developing machine developing machine for dry film manufactured by FujiKiko Co., Ltd.
  • the unexposed part of the photosensitive resin layer was dissolved and removed in a time twice as long as the minimum development time.
  • the shortest time required to completely dissolve the photosensitive resin layer in the unexposed part is the minimum development time.
  • the photosensitive resin composition having the composition shown in Table 1 was sufficiently stirred and mixed, and was uniformly coated on the surface of a 19 ⁇ m thick polyethylene terephthalate film as a support using a bar coater. It was dried in a dryer at 95°C for 4 minutes to form a photosensitive resin layer. Thereafter, the coated surface was visually inspected and graded as follows:
  • the laminated substrate was exposed for 15 minutes using a 21-step step exposure meter manufactured by Stouffer with a 21-step brightness change from transparent to black to evaluate its sensitivity. After exposure, development is carried out at twice the minimum development time, and the exposure amount is 8 according to the stepwise exposure meter in which the resist film is completely left. Carry out the following classification:
  • the exposure is less than 20mJ/cm 2 ;
  • the exposure is 20mJ/cm 2 -50mJ/cm 2 (not including the end value);
  • the exposure level is 50mJ/cm 2 or more.
  • the resolution value is less than 30 ⁇ m
  • the resolution value is 30 ⁇ m-50 ⁇ m (not including the end value);
  • the resolution value is more than 50 ⁇ m.
  • a photosensitive layer (resist layer) with a thickness of 40 ⁇ m and an area of 0.16 m 2 in the photosensitive resin laminate was dissolved in 200 ml of a 1% by mass Na 2 CO 3 aqueous solution, and a circulating spray device was used at a spray pressure of 0.1 MPa Spray for 3 hours. Then, the developer was left for 1 day, and the appearance of aggregates was observed. If agglomerates are present in large quantities, powdery or oily substances can be observed on the bottom or side of the spray device. In addition, aggregates may float in the developer solution.
  • ⁇ There is no agglomerate on the bottom or side of the spraying device. A very small amount of agglomerate can be observed visually floating in the developer, but it can be easily washed off when washing with water;
  • the laminated substrate is exposed for 15 minutes, and then developed with 2 times the minimum development time to form a cured resist normally
  • the minimum mask line width of the line is used as the adhesion value.
  • the adhesion value is less than 30 ⁇ m
  • the adhesion value is 30 ⁇ m-50 ⁇ m (not including the end value);
  • the adhesion value is 50 ⁇ m or more.
  • the product When the EO/PO modified pyrazoline sensitizer of the present invention is applied to a photosensitive resin composition, the product has good compatibility, high sensitivity, high resolution, high solubility, high adhesion, and excellent developability. It has good hydrophilicity during development and can significantly reduce the amount of sludge in the developer during recycling, so that the developer can be used repeatedly and effectively.
  • the photosensitive resin composition can be widely used in the manufacture of printed circuit boards, protective patterns, conductor patterns, lead wires, semiconductor packages, etc., in the form of dry film and wet film.

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Abstract

一种乙氧基/丙氧基改性的吡唑啉有机物、其应用、光固化组合物及光刻胶，-CH 2-CH 2-O(EO)和/或-CH(CH 3)-CH 2-O(PO)的引入使得EO/PO改性吡唑啉类有机物与光固化体系中其它组分具有优异的相溶性，且为固体，添加及使用方便。同时乙氧基/丙氧基改性的吡唑啉有机物的吸收波段在360-400nm之间，特别适合作为增感剂在光固化体系(如含有双咪唑类光引发剂的体系)中使用，能够大大提升光固化体系的感光度。在此基础上，EO/PO改性吡唑啉类有机物具有较高的感性提升性，使用量少，且为固体，添加及使用方便。

Description

乙氧基/丙氧基改性的吡唑啉有机物、其应用、光固化组合物及光刻胶 技术领域
本发明涉及光固化领域，具体而言，涉及一种乙氧基/丙氧基改性的吡唑啉有机物、其应用、光固化组合物及光刻胶。
背景技术
紫外光固化技术因固化速度快、环境污染小等优点得到了广泛应用，其中光引发剂对整个固化体系的固化效率起着决定作用。在实际使用过程中，部分光引发剂由于吸收波长的局限不能很好的引发聚合，往往需要与增感剂配合使用以提高引发效率。增感剂能够将其吸收的能量不断传递给光引发剂，相当于光化学反应的催化剂。然而增感剂的应用受到诸多因素的制约，例如溶解性、吸收波长的匹配性等。现阶段，寻找与光引发剂吸收波长相匹配且相溶性好的增感剂一直是该领域的一个研发热点。
吡唑啉类化合物是一类非常重要的增感剂，已被广泛使用。但现有的这些吡唑啉类化合物在作为增感剂使用时或多或少地存在着溶解性不理想、感光度提升效果不佳等缺点。
干膜显影阶段通常用碱性水溶液洗去未曝光的部分，而吡唑啉类化合物因其极低的溶解性在此时会析出并吸附在电路板表面，如此不仅影响干膜的使用，还会降低产品的精密度，因此后续还需要增加电路板表面清洁工序，致使工艺繁琐，成本大大增加。
现有文献提供了一种吡唑啉大分子类增感剂，解决了溶解度与配方相容性等问题，但在实际应用中发现，存在添加量大、感度提升不足、黏度大使用不方便的问题。因此，存在进一步优化的需要。
发明内容
本发明的主要目的在于提供一种乙氧基/丙氧基改性的吡唑啉有机物、其应用、光固化组合物及光刻胶，以解决现有的吡唑啉大分子类增感剂存在添加量大、感度提升不足、黏度大使用不方便的问题。
为了实现上述目的，根据本发明的一个方面，提供了一种乙氧基/丙氧基改性的吡唑啉有机物，乙氧基/丙氧基改性的吡唑啉有机物具有式(Ⅰ)所示的结构：
Figure PCTCN2021081187-appb-000001
其中，X和Y各自独立地表示-CH 2-CH 2-或-CH(CH 3)-CH 2-；p和q各自独立地表示0～9的整数，且两者不同时为0；R 1表示与吡唑环具有共轭结构的取代基团；R 2表示氢、C 1～C 10的直链或支链烷基、C 4～C 10的烷基环烷基或环烷基烷基；R 3表示氢、C 1～C 20的烃基、或C 6～C 20芳基烷基。
进一步地，p+q≤9；优选地，p+q≤6。
进一步地，R 1选自苯基、萘基、吡咯基、咪唑基、咔唑基、吲哚基、C 2～C 10链烯基、C 4～C 8环二烯基，或，基团中的氢原子可各自独立地被下列基团取代：C 1～C 10的直链或支链烷基、C 4～C 10的烷基环烷基或环烷基烷基、C 3～C 10环烷基、C 6～C 15芳基、C 6～C 12烷基芳基、C 6～C 12芳基烷基、C 2～C 20杂芳基；R 2选自氢、C 1～C 6的直链或支链烷基；R 3选自氢、C 1-C 6的直链或支链烷基、苄基。
进一步地，R 1选自苯基、萘基、吡咯基、咪唑基、咔唑基、吲哚基、C 2～C 6链烯基、C 4～C 6环二烯基、C 1～C 5烷基取代的苯基、C 3～C 6环烷基取代的苯基、C 6～C 10芳基取代链烯基、C 6～C 10烷基芳基取代链烯基、C 6～C 10芳基烷基取代链烯基。
进一步地，R 1选自：
Figure PCTCN2021081187-appb-000002
Figure PCTCN2021081187-appb-000003
进一步地，R 2选自氢、甲基、乙基、丙基、异丙基、丁基、叔丁基或CH 3C(CH 2CH 3) 2-。
进一步地，乙氧基/丙氧基改性的吡唑啉有机物选自以下有机物中的一种或多种：
Figure PCTCN2021081187-appb-000004
本申请的另一方面还提供了一种光固化组合物，包括：(A)碱可溶性聚合物、(B)具有烯属不饱和双键的化合物、(C)第一增感剂、(D)光引发剂和/或第二增感剂、(E)其它任选的助剂，第一增感剂包括上述乙氧基/丙氧基改性的吡唑啉有机物，第二增感剂与第一增感剂的种类不同。
进一步地，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组成的组中的一种或多种。
进一步地，具有烯属不饱和双键的化合物选自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、壬基苯氧基多乙烯氧基丙烯酸酯、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)丙烯酸烷基酯组成的组中的一种或多种。
进一步地，助剂选自供氢体、染料、颜料、光显色剂、填充剂、增塑剂、稳定剂、涂布助剂和剥离促进剂组成的组中的一种或多种。
本申请的又一方面还提供了一种乙氧基/丙氧基改性的吡唑啉有机物在光固化领域中的应用。
本申请的又一方面还提供了一种光刻胶，光刻胶包括上述光固化组合物。
应用本发明的技术方案，由于-CH 2-CH 2-O(EO)和/或-CH(CH 3)-CH 2-O(PO)的引入使得上述EO/PO改性吡唑啉类有机物与光固化体系中其它组分具有优异的相溶性，且为固体，添加及使用方便。同时式(Ⅰ)所示的结构的吸收波段在360-400nm之间，特别适合作为增感剂在光固化体系(如含有双咪唑类光引发剂的体系)中使用，能够大大提升光固化体系的感光度。在此基础上，具有上述结构的EO/PO改性吡唑啉类有机物具有较高的感性提升性，使用量少，且为固体，添加及使用方便。
具体实施方式
需要说明的是，在不冲突的情况下，本申请中的实施例及实施例中的特征可以相互组合。下面将结合实施例来详细说明本发明。
本申请中的术语“淤渣”和“显影垃圾”是指在显影液中积累起来的物质，它不溶于显影液并会再沉积于已显影的基底上，从而降低显影液的效率。
正如背景技术所描述的，现有的吡唑啉大分子类增感剂存在添加量大、感度提升不足、黏度大使用不方便的问题。为了解决上述技术问题，本申请提供了一种乙氧基/丙氧基改性的 吡唑啉有机物，乙氧基/丙氧基改性的吡唑啉有机物具有式(Ⅰ)所示的结构：
Figure PCTCN2021081187-appb-000005
其中，X和Y各自独立地表示-CH 2-CH 2-或-CH(CH 3)-CH 2-；p和q各自独立地表示0～9的整数，且两者不同时为0；R 1表示与吡唑环具有共轭结构的取代基团；R 2表示氢、C 1～C 10的直链或支链烷基、C 4～C 10的烷基环烷基或环烷基烷基；R 3表示氢、C 1～C 20的烃基、或C 6～C 20芳基烷基。
由于-CH 2-CH 2-O(EO)和/或-CH(CH 3)-CH 2-O(PO)的引入使得上述EO/PO改性吡唑啉类有机物具有优异的水溶性或水乳化性能，且为固体，添加及使用方便。同时式(Ⅰ)所示的结构的吸收波段在360-400nm之间，特别适合作为增感剂在光固化体系(如含有双咪唑类光引发剂的体系)中使用，能够大大提升光固化体系的感光度。在此基础上，具有上述结构的EO/PO改性吡唑啉类有机物具有较高的感性提升性，使用量少，且添加及使用方便。
从成本、制备收率等方面考虑，在一种优选的实施方式中，p+q≤9；更优选地，p+q≤6。
为了进一步提高EO/PO改性吡唑啉类有机物的综合性能，在一种优选的实施方式中，R 1选自苯基、萘基、吡咯基、咪唑基、咔唑基、吲哚基、C 2～C 10链烯基、C 4～C 8环二烯基，或，所述基团中的氢原子可各自独立地被下列基团取代：C 1～C 10的直链或支链烷基、C 4～C 10的烷基环烷基或环烷基烷基、C 3～C 10环烷基、C 6～C 15芳基、C 6～C 12烷基芳基、C 6～C 12芳基烷基、C 2～C 20杂芳基；R 2选自氢、C 1～C 6的直链或支链烷基；R 3选自氢、C 1-C 6的直链或支链烷基、苄基。
为了进一步提高R 1与式(Ⅰ)所示增感剂的共轭性，以提高其光灵敏性，优选地，R 1选自苯基、萘基、吡咯基、咪唑基、咔唑基、吲哚基、C 2～C 6链烯基、C 4～C 6环二烯基、C 1～C 5烷基取代的苯基、C 3～C 6环烷基取代的苯基、C 6～C 10芳基取代链烯基、C 6～C 10烷基芳基取代链烯基、C 6～C 10芳基烷基取代链烯基。为了进一步降低EO/PO改性吡唑啉类有机物的合成难度，更优选地，R 1选自以下基团中的一种：
Figure PCTCN2021081187-appb-000006
Figure PCTCN2021081187-appb-000007
为了降低合成难度，同时提高增感剂的水溶性或谁乳化性能，在一种优选的实施例中，R 2选自氢、甲基、乙基、丙基、异丙基、丁基、叔丁基或CH 3C(CH 2CH 3) 2-。
在一种优选的实施例中，乙氧基/丙氧基改性的吡唑啉有机物选自以下有机物中的一种或多种：
Figure PCTCN2021081187-appb-000008
Figure PCTCN2021081187-appb-000009
相比于其它结构的增感剂，上述几种增感剂具有光灵敏度好、使用时粘度适宜、密合性好、合成难度低等优点。
本发明还提供了一种式(Ⅰ)所示的EO/PO改性吡唑啉类增感剂的制备方法，包括以下步骤：
(1)原料a和原料b在含催化剂的溶剂中反应得到中间体A；
(2)中间体A与原料c在强碱作用下反应得到中间体B；
(3)中间体B在酸作用下反应得到中间体C；
(4)中间体C与原料d在冰醋酸中于30-100℃反应2-20h得到中间体D；
(5)原料e和原料f在含缚酸剂的溶剂中反应得到中间体E；
(6)中间体D和中间体E在含缚酸剂的溶剂中反应得到产物F。
反应方程式如下所示：
Figure PCTCN2021081187-appb-000010
Figure PCTCN2021081187-appb-000011
本发明的增感剂是对现有化合物结构的改进和优化。如上述合成路线所示，其制备方法中涉及的合成涉及吡唑啉环结构构建、醚化等，均是有机化学领域的常规工艺。在明确了合成工艺及其原理的情况下，具体的工艺参数对本领域技术人员而言是容易确定的。例如可参见中国专利CN1515557A和国际专利WO2009/060235A中记载的内容，在此将其全文引入以作为参考。
优选地，在步骤(1)中，使用的溶剂并没有特别限定，只要是能够溶解反应试剂且不参与反应的那些常规有机试剂即可，例如二氯甲烷、二氯乙烷、甲苯、苯、二甲苯等。催化剂可选自甲基磺酸、对甲苯磺酸、对甲苯磺酸吡啶盐。反应温度为0～50℃，反应时间通常为2～10h。
优选地，在步骤(2)中，所述的强碱是氢氧化钾或氢氧化钠等。反应在有机溶剂中进行，对溶剂种类没有特别限定，一般为甲醇、乙醇等醇类溶剂。反应温度和反应时间根据原料c的结构不同而有所差异，通常而言，反应温度为0～80℃，反应时间通常为2～10h。
优选地，在步骤(3)中，该反应是一个水解反应过程，典型地，可将中间体B溶于含有酸的诸如二氯甲烷、二氯乙烷等烃类溶剂中进行。所述的酸可以是盐酸、醋酸、甲磺酸等。反应温度为0～50℃，反应时间通常为1～10h。
优选地，在步骤(5)中，对使用的溶剂种类并没有特别限定，只要能够溶解反应原料且对反应无不良影响即可，例如二氯甲烷、二氯乙烷、乙腈、N,N-二甲基甲酰胺等。所述缚酸剂可以是碳酸钠、氢氧化钠、碳酸钾、甲醇钠、吡啶、三乙胺等。反应温度为0～100℃，反应时间通常为1～6h。
优选地，在步骤(6)中，对使用的溶剂种类并没有特别限定，只要能够溶解反应原料且对反应无不良影响即可，例如乙腈、N,N-二甲基甲酰胺、N,N-二乙基甲酰胺等。所述缚酸剂可以是碳酸钠、氢氧化钠、碳酸钾、甲醇钠、吡啶、三乙胺等。反应温度为60～140℃，反应时间通常为4～10h。
本申请的另一方面还提供了一种光固化组合物，包括：(A)碱可溶性聚合物、(B)具有烯属不饱和双键的化合物、(C)增感剂、(D)光引发剂、(E)其它助剂，增感剂包括式(Ⅰ)所示的增感剂。
本发明的上述EO/PO改性吡唑啉类增感剂溶解性能优异，吸收波段在360-400nm之间，特别适合作为增感剂在光固化体系特别是含有双咪唑类光引发剂的体系中使用，对感光度的提升效果优异。本发明的上述EO/PO改性吡唑啉类增感剂应用于感光性树脂组合物时，组合物具有相容性好、感光度高、分辨率高、附着力高、显影性优异的特点，且显影时具有较好的亲水性，能显著减少循环使用时显影液中的淤渣量，使得显影液可重复多次、有效使用。
本发明的EO/PO改性吡唑啉类增感剂可水溶或水可乳化，该特性消除或至少减少了显影剂和剥离剂溶液中浮渣和残余物的积累以及未固化光致抗蚀剂在设备和印刷电路板上浮渣和残余物的沉积，能够提高印刷电路板的良率。
(A)碱可溶性聚合物
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适用，并没有特别的限制。
在一种优选的实施例中，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组成的组中的一种或多种。
在一种优选的实施例中，上述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，包括但不限于：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)丙烯酸酯类化合物；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。
从碱显影性和密合性的角度考虑，为了提高碱可溶性聚合物的碱显影性和密合性，优选使用含羧基的碱可溶性聚合物，上述具有羧基的碱可溶性聚合物包括但不限于：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；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；以及除(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。
在另一种优选的实施例中，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它可共聚单体共聚而成的(甲基)丙烯酸酯系聚合物。
上述(甲基)丙烯酸酯包括但不限于：(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)丙烯酸缩水甘油酯等。这些(甲基)丙烯酸酯可以单独使用，也可以两种以上组合使用。
上述乙烯性不饱和羧酸包括但不限于：丙烯酸、甲基丙烯酸、丁烯酸、马来酸、富马酸、衣康酸，优选为丙烯酸、甲基丙烯酸。这些乙烯性不饱和羧酸可以单独使用，也可以两种以上组合使用。
上述其它可共聚单体包括但不限于：(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。这些其它可共聚单体可以单独使用，也可以两种以上组合使用。
上述碱可溶性聚合物可以单独一种使用，也可以两种以上组合使用。作为组合两种以上使用的碱可溶性聚合物，可以为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。
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，其应与具体应用环境相适应。从机械强度与碱显影性方面综合考虑，为了进一步提高碱可溶性聚合物的碱显影性能和其成膜后的机械强度，优选地，碱可溶性聚合物的重均分子量优选为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。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。
从碱显影性良好的角度考虑，碱可溶性树脂的酸值较小时，碱可溶性树脂的显影速度较慢；酸值较大时，碱可溶性树脂的密合性较小，显影后，易出现组合物贮存稳定性降低、粘度上升的问题。为了进一步提高碱可溶性聚合物的显影性能和密合性，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70～250mg KOH/g，特别优选为100～250mgKOH/g。
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。
在100重量份感光性树脂组合物中，碱可溶性聚合物在组合物中的含量优选为20～70重量份，更优选30～60重量份。当碱可溶性聚合物的含量在20重量份以上，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重量份以下，有利于提高感光性树脂组合物的灵敏度。
(B)具有烯属不饱和双键的化合物
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。对具有烯属不饱和双键的化合物没有特别限定，只要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就可以使用。优选地，具有烯属不饱和双键的化合物包括但不限于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、壬基苯氧基多乙烯氧基丙烯酸酯、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)丙烯酸烷基酯组成的组中的一种或多种。相比于其它种类的有烯属不饱和双键的化合物，选用上述几种有利于进一步提高感光性树脂的成膜性，并降低其成本。
在一种优选的实施例中，上述α,β-不饱和羧酸与多元醇反应而得的化合物包括但不限于：亚乙基数为2-14的聚乙二醇二(甲基)丙烯酸酯、亚丙基数为2-14的聚丙二醇二(甲基)丙烯酸酯、亚乙基数为2-14且亚丙基数为2-14的聚亚乙基·聚亚丙基二醇二(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)丙烯酸酯组成的组中的一种或多种。
在另一种优选的实施例中，双酚A类(甲基)丙烯酸酯化合物包括但不限于：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。
更优选地，上述2,2-双{4-[(甲基)丙烯酰氧基多乙氧基]苯基}丙烷包括但不限于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}丙烷组成的组中的一种或多种。
更优选地，上述2,2-双{4-[(甲基)丙烯酰氧基多乙氧基]苯基}丙烷的1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，也可两种以上组合使用。
在一种优选的实施例中，上述分子内具有氨酯键的(甲基)丙烯酸酯化合物包括但不限于：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)丙烯酸酯等。其中，二异氰酸酯化合物包括但不限于异佛尔酮二异氰酸酯、2,6-甲苯二异氰酸酯、2,4-甲苯二异氰酸酯和1,6-六亚甲基二异氰酸酯组成的组中的一种或多种。
在一种优选的实施例中，上述壬基苯氧基多乙烯氧基丙烯酸酯包括但不限于：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组成的组中的一种或多种。
在一种优选的实施例中，上述苯二甲酸类化合物包括但不限于：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组成的组中的一种或多种。
在一种优选的实施例中，上述(甲基)丙烯酸烷基酯但不限于(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)丙烯酸酯组成的组中的一种或多种。更优选地，(甲基)丙烯酸烷基酯包括但不限于(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组成的组中的一种或多种。
从提高分辨率、耐镀覆性、密合性的角度来看，为了提高感光性树脂的分辨率、耐镀覆性、密合性，优选地，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/或分子内具有氨酯键的(甲基)丙烯酸酯化合物。
从可以提高灵敏度和解析度的角度来看，为了提高感光性树脂的灵敏度和解析度，优选地，具有烯属不饱和双键的化合物为双酚A类(甲基)丙烯酸酯化合物。
双酚A类(甲基)丙烯酸酯化合物的市售品包括但不限于：2,2-双{4-[(甲基)丙烯酰氧基多乙氧基]苯基}丙烷(新中村化学工业株式会社制，BPE-200)、2,2-双{4-[(甲基)丙烯酰氧基多丙氧基]苯基)丙烷(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(新中村化学工业株式会社，BPE-1300)等。
在一种优选的实施例中，在100重量份感光性树脂组合物中，具有烯属不饱和双键的化合物(B)的含量为20～50重量份，更优选25～45重量份。当所述具有烯属不饱和双键的化合物的含量在20重量份以上时，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重量份以下，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。
第一增感剂(C)
上述第一增感剂(C)为上述EO/PO改性吡唑啉类增感剂中的一种或多种，结构如上文所述。
为了进一步提高光固化组合物的增感性，优选地，在100重量份感光性树脂组合物中，第一增感剂(C)(EO/PO改性吡唑啉类增感剂)的含量为0.001～10重量份，优选0.005～5重量份。若含量过小，存在光致灵敏度下降的缺陷；如果含量过大，则存在光阻图案趋于变宽超过光掩模线宽的缺陷。将增感剂的用量限定在上述范围内有利于提高光固化组合物的光致灵敏度和清晰度。
其它光引发剂和/或第二增感剂(D)
上述感光性组合物中除了包括上述EO/PO改性吡唑啉类增感剂之外，还可以包括光引发剂和其它种类的增感剂，光引发剂也可以采用本领域常用的种类。上述光引发剂和/或第二增感剂包括但不限于：双咪唑类有机物、吖啶类有机物、芳香族酮类有机物、蒽醌类有机物、苯偶姻和苯偶姻烷基醚类有机物、肟酯类有机物、三嗪类有机物、香豆素类有机物、噻吨酮类有机物中的一种或多种。
在一种优选的实施例中，双咪唑类化合物包括但不限于：2,2’-二(邻氯苯基)-4,4’,5,5’-四苯基-二咪唑、2,2’,5-三(邻氯苯基)-4-(3,4-二甲氧基苯基)-4’,5’-二苯基-1,1’-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-(邻氯苯基)-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(邻氯苯基)-二咪唑、2,2’-二(2-氯-5-硝基苯基)-4-(3,4-二甲氧基苯基)-5-(邻氯苯基)-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(邻氯苯基)-二咪唑、2-(2,4-二氯苯基)-4-(3,4-二甲氧基苯基)-2’,5-二(邻氯苯基)-4’,5’-二苯基-二咪唑、2-(2,4-二氯苯基)-2’-(邻氯苯基)-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。这些双咪唑类化合物可以单独使用或两种以上组合使用。
在一种优选的实施例中，吖啶类化合物包括但不限于：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、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。这些吖啶类化合物可以单独使用或两种以上组合使用。
在一种优选的实施例中，芳香族酮类化合物包括但不限于：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。这些芳香族酮类化合物可以单独使用或两种以上组合使用。
在一种优选的实施例中，蒽醌类化合物包括但不限于：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。这些蒽醌类化合物可以单独使用或两种以上组合使用。
在一种优选的实施例中，苯偶姻和苯偶姻烷基醚类化合物包括但不限于：苯偶姻甲基醚、苯偶姻乙基醚、苯偶姻苯基醚。这些苯偶姻和苯偶姻烷基醚类化合物可以单独使用或两种以上组合使用。
在一种优选的实施例中，肟酯类化合物包括但不限于：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。这些肟酯类化合物可以单独使用或两种以上组合使用。
在一种优选的实施例中，三嗪类化合物包括但不限于：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、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。这些三嗪类化合物可以单独使用或两种以上组合使用。
在一种优选的实施例中，香豆素类化合物但不限于：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。这些香豆素类化合物可以单独使用或两种以上组合使用。
在一种优选的实施例中，噻吨酮类化合物包括但不限于：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。这些噻吨酮类化合物可以单独使用或两种以上组合使用。
在一种优选的实施例中，香豆素类化合物包括但不限于：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。这些香豆素类化合物可以单独使用或两种以上组合使用。
在一种优选的实施例中，噻吨酮类化合物包括：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。这些噻吨酮类化合物可以单独使用或两种以上组合使用。
在一种优选的实施例中，在100重量份感光性树脂组合物中，其它光引发剂和/或第二增感剂(D)的总含量为0.01～10重量份。
(E)其它助剂
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。在一种优选的实施例中，助剂包括但不限于供氢体、染料、颜料、光显色剂、填充剂、增塑剂、稳定剂、涂布助剂、剥离促进剂中的一种或多种。
上述光固化组合物中，供氢体在具体种类方面没有特别限制。优选地，供氢体包括但不限于：胺类化合物、羧酸类化合物、含有巯基的有机硫化合物或醇类化合物。这些化合物可单独使用，或以其中的两种及以上组合使用。可选地，供氢体包括但不限于：三乙醇胺、4-二甲氨基苯甲酸甲酯、4,4’-双(二甲氨基)二苯甲酮、4,4’-双(二乙氨基)二苯甲酮、苯基硫代乙酸、甲基苯基硫代乙酸、乙基苯基硫代乙酸、二甲氧基苯基硫代乙酸、氯苯基硫代乙酸、二 氯苯基硫代乙酸、N-苯基甘氨酸、苯氧基乙酸、萘基硫代乙酸、N-萘基甘氨酸、萘氧基乙酸、2-巯基苯并噻唑(MBO)、2-巯基苯并咪唑(MBI)、十二烷基硫醇、乙二醇双(3-巯基丁酸酯)等。
在一种优选的实施例中，染料、颜料及光显色剂包括但不限于：三(4-二甲基氨基苯基)甲烷(即隐色结晶紫，LCV)、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、酞菁系染料(如酞菁绿和/或酞菁蓝)、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、N，N-二乙基苯胺、二-对伸二胺、对甲苯胺、苯并三氮唑、甲基苯丙三唑、4,4’-联二胺、邻氯苯胺、白色结晶紫、白色孔雀绿、白色苯胺、白色甲基紫、偶氮系染料以及二氧化钛。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。
在一种优选的实施例中，填充剂包括但不限于：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。
在一种优选的实施例中，增塑剂包括但不限于：邻苯二甲酸酯(如邻苯二甲酸二丁酯、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)，磺酰胺类有机物(如三甘醇二乙酸酯、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)、磷酸酯类有机物(如磷酸三苯酯、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)、醇酯类有机物(如二辛酸三甘醇酯、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)、Brij30(C 12H 25(OCH 2CH 2) 4OH)、和Brij35(C 12H 25(OCH 2CH 2) 20OH)等。在上述光固化组合物中，增塑剂可以单独一种使用，也可两种以上混合使用。
在一种优选的实施例中，稳定剂包括但不限于：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。在上述光固化组合物中，稳定剂可以单独一种使用，也可两种以上混合使用。
在一种优选的实施例中，涂布助剂包括但不限于：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。在上述光固化组合物中，涂布助剂可以单独一种使用，也可两种以上混合使用。
在一种优选的实施例中，剥离促进剂包括(但不限于)：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。在上述光固化组合物中，剥离促进剂可以单独一种使用，也可两种以上混合使用。
在一种优选的实施例中，在100重量份感光性树脂组合物中，其它助剂的含量为1～10重量份。
本申请的又一方面还提供了一种式(Ⅰ)乙氧基/丙氧基改性的吡唑啉有机物在光固化领域中的应用。
由于-CH 2-CH 2-O(EO)和/或-CH(CH 3)-CH 2-O(PO)的引入使得上述EO/PO改性吡唑啉类有机物具有优异的水溶性或水乳化性能，且为固体，添加及使用方便。同时式(Ⅰ)所示的结构的吸收波段在360-400nm之间，特别适合作为增感剂在光固化体系(如含有双咪唑类光引发剂的体系)中使用，能够大大提升光固化体系的感光度。在此基础上，具有上述结构的EO/PO改性吡唑啉类有机物具有较高的感性提升性，使用量少，且添加及使用方便。
<干膜和湿膜应用>
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。
本发明的感光性树脂组合物也可以通过湿膜涂布机直接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。
干膜应用
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。
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)。优选地，上述干燥步骤的干燥条件是在60～100℃下干燥0.5～15min。感光性树脂层的厚度优选为5～95μm。感光性树脂的厚度包括但不限于上述范围，而将其限定在上述范围内有利于提高其绝缘性和解析性。更优选地，感光性树脂的厚度为10～50μm，进一步优选为15～30μm。
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。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。
对感光性树脂组合物的涂布方式并无特殊限制，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。
在一种优选的实施方式中，本发明提供上述干膜在制造印刷电路板中的应用，包括：
(1)层叠工序：将感光性树脂层叠体层叠于基板上；
(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；
(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；
(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；
(5)剥离工序：将保护图案从该覆铜层叠板或柔性基板剥离。
在一种优选的实施例中，层叠工序中采用的基板包括但不限于覆铜层叠板、柔性基板、金属板、金属覆膜绝缘板和具有大规模集成电路的晶片中的一种或多种。
本发明提供上述干膜在制造半导体封装中的应用，当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。当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。
湿膜应用
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。
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。
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。
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。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。
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，然后再使用显影液(如碱性水溶液、水系显影液、有机溶剂等)除去未曝光部分。优选地，碱性水溶液包括但不限于0.1-5重量％的碳酸钠溶液、0.1～5重量％的碳酸钾溶液或0.1～5重量％的氢氧化钠溶液，pH值优选为9～11。更优选地，上述碱性水溶液还包括表面活性剂、消泡剂或有机溶剂中的一种或多种。显影的方式包括但不限于浸渍、喷雾、刷洗等常规方式。
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。
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。镀敷处理的方法包括但不限于电镀处理，或无电解镀覆处理，优选为无电解镀覆处理。更优选地，无电解镀覆处理包括但不限于：铜镀敷(硫酸铜镀敷和/或焦磷酸铜镀敷)、焊锡镀敷(如高均匀焊锡(high-throw solder)镀敷)、镍镀敷(瓦特浴(硫酸镍-氯化镍)镀敷和/或氨基磺酸镍镀敷)、或金镀敷(硬质金镀敷和/或软质金镀敷)。
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重量％的氢氧化钠水溶液。
以下结合具体实施例对本申请作进一步详细描述，这些实施例不能理解为限制本申请所要求保护的范围。
1.EO/PO改性吡唑啉类增感剂的制备
1.1产物C1的制备
1.1.1中间体A的制备
Figure PCTCN2021081187-appb-000012
向四口烧瓶中依次投入183.1g对羟基苯甲醛、5.0g对甲苯磺酸吡啶盐、300.0mL二氯乙烷，控温45±5℃滴加126.0g二氢吡喃，滴加时间约1h，滴加完毕后继续搅拌2h。HPLC中控反应进程，对羟基苯甲醛剩余小于1％时，结束保温。向反应体系中缓慢滴加52.0g 30％氢氧化钠水溶液，分去水层，下层有机层用100.0g纯水洗涤一次，旋蒸除去二氯甲烷，得到275.2g中间体A，纯度98.12％，直接用于下步反应。
使用LCMS确认中间体A的结构，质谱分析借助仪器附带软件得到207与208分子碎片峰，产品的分子量为206，与T+1和T+2吻合。
1.1.2中间体B的制备
Figure PCTCN2021081187-appb-000013
向四口烧瓶中依次投入247.1g中间体A、235.2g联苯乙酮、300.0mL甲醇，控温25±5℃滴加80.0g 40％氢氧化钠水溶液，滴加时间约2h，滴加完毕后继续搅拌6h。HPLC中控反应进程，联苯乙酮剩余小于1％时，结束保温。过滤得415.6g中间体B，纯度93.65％，直接用于下步反应。
使用LCMS确认中间体B的结构，质谱分析借助仪器附带软件得到385与386分子碎片峰，产品的分子量为384，与T+1和T+2吻合。
1.1.3中间体C的制备
Figure PCTCN2021081187-appb-000014
向四口烧瓶中依次投入384.4g中间体B、50.0g 37％的浓盐酸、500.0mL二氯乙烷，控温25±5℃继续搅拌6h。HPLC中控反应进程，中间体B剩余小于1％时，结束保温。过滤，烘干得210.5g中间体C，纯度98.95％。
使用LCMS确认中间体B的结构，质谱分析借助仪器附带软件得到301与302分子碎片峰，产品的分子量为300，与T+1和T+2吻合。
1.1.4中间体D的制备
Figure PCTCN2021081187-appb-000015
向四口烧瓶中依次投入180.0g中间体C、500.0mL冰醋酸，控温50±5℃滴加108.0g苯肼，滴加时间约2h，滴加完毕后继续搅拌8h。过滤，甲醇重结晶，烘干得214.5g中间体D，纯度99.65％。
使用LCMS确认中间体B的结构，质谱分析借助仪器附带软件得到391与392分子碎片峰，产品的分子量为390，与T+1和T+2吻合。
1.1.5中间体E的制备
Figure PCTCN2021081187-appb-000016
向四口烧瓶中依次投入56.1g对甲苯磺酰氯、50.0g三乙二醇单甲醚、200.0g二氯甲烷和0.5g 4-二甲氨基吡啶，升温至30℃后，滴加34.0g三乙胺，约30min滴加完毕，然后保温反应。HPLC中控反应进程，对甲苯磺酰氯剩余小于1％时，结束保温。反应液抽滤后，滤液用100g纯水水洗3次，用无水硫酸钠干燥后，过滤，浓缩，得到80.3g中间体E，纯度96.51％。无需做进一步提纯，直接用于下一步反应。
使用LCMS确认中间体E的结构，质谱分析借助仪器附带软件得到319与320分子碎片峰，产品的分子量为318，与T+1和T+2吻合。
1.1.6产物C1的制备
Figure PCTCN2021081187-appb-000017
向四口烧瓶中依次投入68.0g中间体E、250.0g乙腈、73.6g中间体D和49.1g碳酸钾，开启搅拌，升温至80℃，保温反应。HPLC中控反应进程，中间体D剩余小于1％时，结束保 温。加入300g纯水和300g乙酸乙酯，分去水层，上层有机层用水洗涤二次，减压蒸馏乙酸乙酯至一倍量后，加入100mL甲醇，过滤，烘干后得到92.2g产物C1，纯度99.12％。
使用LCMS确认产物C1的结构，质谱分析借助仪器附带软件得到537与538分子碎片峰，产品的分子量为536，与T+1和T+2吻合。
使用核磁进一步确认产物C1的结构，数据如下：
1H NMR(400MHz,DMSO-d6)7.83(d,2H),7.74(d,4H),7.49(t,2H),7.39(t,1H),7.22(d,2H),7.17(t,2H),7.05(d,2H),6.91(d,2H),6.73(t,1H),5.46(dd,1H),4.06(t,2H),3.71(t,2H),3.57(d,2H),3.56-3.22(m,8H),3.14(s,3H)ppm。
1.2产物C2的制备
Figure PCTCN2021081187-appb-000018
参照产物C1的合成方法，将原料f即三乙二醇单甲醚替换成三丙二醇单甲醚，得产物C2，纯度99.28％。
使用LCMS确认产物C2的结构，质谱分析借助仪器附带软件得到579与580分子碎片峰，产品的分子量为578，与T+1和T+2吻合。
使用核磁进一步确认产物C2的结构，数据如下：
1H NMR(400MHz,DMSO-d6)7.85(d,2H),7.74(d,4H),7.50(t,2H),7.38(t,1H),7.25(d,2H),7.13(t,2H),7.04(d,2H),6.96(d,2H),6.73(t,1H),5.47(dd,1H),4.06(m,1H),3.71(m,2H),3.56-3.22(m,17H),3.19(s,3H)ppm。
1.3产物C3的制备
Figure PCTCN2021081187-appb-000019
参照产物C1的合成方法，将原料f即三乙二醇单甲醚替换成三乙二醇单苄醚，得产物C3，纯度99.54％。
使用LCMS确认产物C3的结构，质谱分析借助仪器附带软件得到613与614分子碎片峰，产品的分子量为612，与T+1和T+2吻合。
使用核磁进一步确认产物C3的结构，数据如下：
1H NMR(400MHz,DMSO-d6) 1H NMR(400MHz,DMSO-d6)7.84(d,2H),7.77(d,4H),7.63(d,2H),7.45(t,2H),7.39(t,3H),7.25(d,2H),7.15(t,2H),7.02(d,2H),6.95(d,2H),6.72(t,1H),5.48(dd,1H),4.17(s,2H),4.02(t,2H),3.78(t,2H),3.53(d,2H),3.66-3.32(m,8H)ppm。
1.4产物C4的制备
Figure PCTCN2021081187-appb-000020
参照产物C1的合成方法，将原料a即对羟基苯甲醛替换成间羟基苯甲醛，得产物C4，纯度99.17％。
使用LCMS确认产物C4的结构，质谱分析借助仪器附带软件得到537与538分子碎片峰，产品的分子量为536，与T+1和T+2吻合。
使用核磁进一步确认产物C4的结构，数据如下：
1H NMR(400MHz,DMSO-d6)7.89(d,2H),7.78(d,2H),7.70(s,1H),7.61(t,2H),7.54(t,2H),7.35(t,1H),7.29(d,2H),7.21(t,2H),7.14(d,2H),6.98(d,2H),6.80(t,1H),5.52(dd,1H),4.14(t,2H),3.82(t,2H),3.64(d,2H),3.59-3.24(m,8H),3.23(s,3H)ppm。
1.5产物C5的制备
Figure PCTCN2021081187-appb-000021
参照产物C1的合成方法，将原料c即联苯乙酮替换成对叔丁基苯甲醛，得产物C5，纯度99.49％。
使用LCMS确认产物C5的结构，质谱分析借助仪器附带软件得到543与544分子碎片峰，产品的分子量为542，与T+1和T+2吻合。
使用核磁进一步确认产物C5的结构，数据如下：
1H NMR(400MHz,DMSO-d6)7.84(s,1H),7.76(d,2H),7.44(d,2H),7.39(t,2H),7.33(d,2H),7.04(s,1H),7.02(t,1H),6.91(d,2H),6.80(d,2H),5.29(dd,1H),4.33(t,2H),3.89(t,2H),3.59-3.42(m,10H),3.40(s,3H),1.36(s,9H)ppm。
1.6产物C6的制备
Figure PCTCN2021081187-appb-000022
参照产物C1的合成方法，将原料c即联苯乙酮替换成1-萘乙酮，得产物C6，纯度99.33％。
使用LCMS确认产物C6的结构，质谱分析借助仪器附带软件得到511与512分子碎片峰，产品的分子量为510，与T+1和T+2吻合。
使用核磁进一步确认产物C6的结构，数据如下：
1H NMR(400MHz,DMSO-d6)8.50(d,1H),8.52(d,1H),7.99(t,1H),7.94(d,2H),7.73(t,1H),7.43(t,1H),7.34-7.21(m,4H),7.13-6.81(m,5H),5.43(dd,1H),4.11(t,2H),3.72(t,2H),3.58(d,2H),3.65-3.25(m,8H),3.17(s,3H)ppm。
2.感光性树脂组合物的制备
参照表1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1中所示份数均为重量份。
表1
Figure PCTCN2021081187-appb-000023
Figure PCTCN2021081187-appb-000024
表1中各组分代号表示的含义如下表2中所示。
表2
Figure PCTCN2021081187-appb-000025
3性能评价
3.1评价方式
<干膜的制作>
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。
<基板表面整平>
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]。
<层压>
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。
<曝光>
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)，以60mJ/cm 2的照射能量曝光感光层。
<显影>
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。
3.2评价内容
(1)相容性评价
将具有表1所示组成的感光性树脂组合物充分搅拌、混合，使用棒涂布器均匀地涂布于作为支撑体的19μm厚的聚对苯二甲酸乙二醇酯薄膜的表面上。在95℃的干燥机中干燥4min，形成感光性树脂层。此后，目测涂布表面，按以下方式分级：
○：涂布面均匀；
●：涂布面上析出未溶物。
(2)感光度评价
使用具有从透明到黑色的21级明亮度变化的Stouffer制造的21级阶段式曝光表对层压后基板曝光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：
○：曝光量为20mJ/cm 2以下；
◎：曝光量为20mJ/cm 2-50mJ/cm 2(不包括端值)；
●：曝光量为50mJ/cm 2以上。
(3)分辨率评价
通过曝光部分和未曝光部分的宽度为1:1的比率的线型图案掩模，对层压后的基板曝光15min，然后用最小显影时间的2倍时间进行显影，以正常形成固化抗蚀线的最小掩模线宽作为分辨率值。进行如下分级：
○：分辨率值为30μm以下；
◎：分辨率值为30μm-50μm(不包括端值)；
●：分辨率值为50μm以上。
(4)显影性评价
使感光性树脂层合体中厚度为40μm，面积为0.16m 2的感光层(抗蚀剂层)溶解在200ml的1质量％Na 2CO 3水溶液中，使用循环式喷射装置在喷射压0.1MPa下喷射3小时。然后，将显影液放置1天，观察凝集物的出现。如果凝集物大量出现，则可在喷射装置的底部或侧面观察到粉末状或油状物质。另外，有时在显影液中漂浮有凝集物。显影液凝集性良好的组成，则完全不出现这些凝集物，或即使出现，也可以通过极微量水的洗涤从喷射装置中简单地冲洗掉。通过目视观察凝集物的出现状态，按以下方式进行分级：
○：在喷射装置的底部或侧面没有凝集物，可观察到显影液中漂浮有可目视确认的极微量凝集物，但水洗时可简单地冲洗掉；
◎：喷射装置的底部或侧面的一部分及显影液中漂浮有凝集物，即使进行水洗也不能完全部洗掉；
●：喷射装置整体可见凝集物且显影液中漂浮有凝集物。即使进行水洗也不能完全洗掉，大部分残留下来。
(5)附着力评价
通过曝光部分和未曝光部分的宽度为1:100的比率的线型图案掩模，对层压后的基板曝光15min，然后用最小显影时间的2倍显影时间进行显影，以正常形成固化抗蚀线的最小掩模线宽作为附着力值。
○：附着力值为30μm以下；
◎：附着力值为30μm-50μm(不包括端值)；
●：附着力值为50μm以上。
3.3评价结果
评价结果如表3中所示。
表3
  相容性 感光度 分辨率 显影性 附着力
实施例1 ○ 15/○ 25/○ ○ 25/○
实施例2 ○ 16/○ 26/○ ○ 28/○
实施例3 ○ 16/○ 28/○ ○ 26/○
实施例4 ○ 15/○ 27/○ ○ 26/○
实施例5 ○ 18/○ 28/○ ○ 28/○
实施例6 ○ 18/○ 27/○ ○ 27/○
比较例1 ● 31/◎ 42/◎ ● 40/◎
本发明的EO/PO改性吡唑啉类增感剂应用于感光性树脂组合物时，产物相容性好、感光度高、分辨率高、溶解性高、附着力高、显影性优异，显影时具有较好的亲水性，能显著减少循环使用时显影液中的淤渣量，使得显影液可重复多次、有效使用。该感光性树脂组合物能够以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。
以上所述仅为本发明的优选实施例而已，并不用于限制本发明，对于本领域的技术人员来说，本发明可以有各种更改和变化。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (13)

  1. 一种乙氧基/丙氧基改性的吡唑啉有机物，其特征在于，所述乙氧基/丙氧基改性的吡唑啉有机物具有式(Ⅰ)所示的结构：
    Figure PCTCN2021081187-appb-100001
    其中，所述X和Y各自独立地表示-CH 2-CH 2-或-CH(CH 3)-CH 2-；
    p和q各自独立地表示0～9的整数，且两者不同时为0；
    R 1表示与吡唑环具有共轭结构的取代基团；
    R 2表示氢、C 1～C 10的直链或支链烷基、C 4～C 10的烷基环烷基或环烷基烷基；
    R 3表示氢、C 1～C 20的烃基、或C 6～C 20芳基烷基。
  2. 根据权利要求1所述的乙氧基/丙氧基改性的吡唑啉有机物，其特征在于，所述p+q≤9；优选地，p+q≤6。
  3. 根据权利要求1或2所述的乙氧基/丙氧基改性的吡唑啉有机物，其特征在于，所述R 1选自苯基、萘基、吡咯基、咪唑基、咔唑基、吲哚基、C 2～C 10链烯基、C 4～C 8环二烯基，或，所述基团中的氢原子可各自独立地被下列基团取代：C 1～C 10的直链或支链烷基、C 4～C 10的烷基环烷基或环烷基烷基、C 3～C 10环烷基、C 6～C 15芳基、C 6～C 12烷基芳基、C 6～C 12芳基烷基、C 2～C 20杂芳基；
    所述R 2选自氢、C 1～C 6的直链或支链烷基；
    所述R 3选自氢、C 1～C 6的直链或支链烷基、苄基。
  4. 根据权利要求3所述的乙氧基/丙氧基改性的吡唑啉有机物，其特征在于，所述R 1选自苯基、萘基、吡咯基、咪唑基、咔唑基、吲哚基、C 2～C 6链烯基、C 4～C 6环二烯基、C 1～C 5烷基取代的苯基、C 3～C 6环烷基取代的苯基、C 6～C 10芳基取代链烯基、C 6～C 10烷基芳基取代链烯基、C 6～C 10芳基烷基取代链烯基。
  5. 根据权利要求4所述的乙氧基/丙氧基改性的吡唑啉有机物，其特征在于，所述R 1选自：
    Figure PCTCN2021081187-appb-100002
    Figure PCTCN2021081187-appb-100003
  6. 根据权利要求2至5中任一项所述的乙氧基/丙氧基改性的吡唑啉有机物，其特征在于，所述R 2选自氢、甲基、乙基、丙基、异丙基、丁基、叔丁基或CH 3C(CH 2CH 3) 2-。
  7. 根据权利要求6所述的乙氧基/丙氧基改性的吡唑啉有机物，其特征在于，所述乙氧基/丙氧基改性的吡唑啉有机物选自以下有机物中的一种或多种：
    Figure PCTCN2021081187-appb-100004
    Figure PCTCN2021081187-appb-100005
  8. 一种光固化组合物，其特征在于，包括：(A)碱可溶性聚合物、(B)具有烯属不饱和双键的化合物、(C)第一增感剂、(D)光引发剂和/或第二增感剂、(E)其它任选的助剂，所述第一增感剂为权利要求1至7中任一项所述的乙氧基/丙氧基改性的吡唑啉有机物，所述第二增感剂与所述第一增感剂的种类不同。
  9. 根据权利要求8所述的光固化组合物，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组成的组中的一种或多种。
  10. 根据权利要求9所述的光固化组合物，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、壬基苯氧基多乙烯氧基丙烯酸酯、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)丙烯酸烷基酯组成的组中的一种或多种。
  11. 根据权利要求9或10所述的光固化组合物，其特征在于，所述助剂选自供氢体、染料、颜料、光显色剂、填充剂、增塑剂、稳定剂、涂布助剂和剥离促进剂组成的组中的一种或多种。
  12. 权利要求1至7中任一项所述的乙氧基/丙氧基改性的吡唑啉有机物在光固化领域中的应用。
  13. 一种光刻胶，其特征在于，所述光刻胶包括权利要求8至11中任一项所述的光固化组合物。
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CN113527207A (zh) 2021-10-22
JP7465998B2 (ja) 2024-04-11
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