WO2022089228A1 - 固化性树脂组合物、及其形成的阻焊膜、层间绝缘材料和印刷电路板 - Google Patents

固化性树脂组合物、及其形成的阻焊膜、层间绝缘材料和印刷电路板 Download PDF

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Publication number
WO2022089228A1
WO2022089228A1 PCT/CN2021/124164 CN2021124164W WO2022089228A1 WO 2022089228 A1 WO2022089228 A1 WO 2022089228A1 CN 2021124164 W CN2021124164 W CN 2021124164W WO 2022089228 A1 WO2022089228 A1 WO 2022089228A1
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Prior art keywords
photopolymerization initiator
resin composition
curable resin
group
compounds
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PCT/CN2021/124164
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English (en)
French (fr)
Inventor
严春霞
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常州正洁智造科技有限公司
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Publication of WO2022089228A1 publication Critical patent/WO2022089228A1/zh

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings
    • H05K3/282—Applying non-metallic protective coatings for inhibiting the corrosion of the circuit, e.g. for preserving the solderability
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings
    • H05K3/285—Permanent coating compositions
    • H05K3/287—Photosensitive compositions

Definitions

  • the present invention relates to the field of photocuring, in particular, to a curable resin composition, a solder resist film, an interlayer insulating material and a printed circuit board formed therefrom.
  • the printed wiring board has a conductor circuit pattern formed on a base material, electronic components are mounted on the pad portion of the conductor circuit by soldering, and the circuit portion other than the pad portion is covered with a solder resist to protect the conductor.
  • the solder resist film used in the manufacturing process of the printed circuit board can not only protect the unrelated wiring during the soldering process, but also can be used as a plating protective layer during the plating process. Therefore, the solder resist film needs to have advantages such as heat resistance during soldering, chemical resistance during plating treatment, and insulation reliability after soldering. In addition, solder mask also reduces the risk of poor appearance of copper circuits due to heat, moisture or electricity, damage, dirt, etc.
  • UV-LED lamps are usually used as curing light sources instead of conventional UV lamps.
  • UV-LED light has a long wavelength, the curing performance is low, and the curable resin composition cannot be cured sufficiently compared with the conventional UV lamps, which requires further improvement of the curability of the curable resin composition.
  • a copper circuit is formed on the substrate, when solder resist or laminated solder resist is applied to it, the distribution law of the thickness of the resist film is thick on the substrate, thin on the copper circuit, and thin on the copper circuit. part of the edge is thinner. In the face of the above-mentioned situation of different thicknesses of the solder mask, when curing with a UV-LED light source, the defect that cannot be fully cured will become more obvious.
  • the main purpose of the present invention is to provide a curable resin composition, and the solder resist film, interlayer insulating material and printed circuit board formed therefrom, so as to solve the problem that the existing curable composition cannot be fully cured under UV-LED light source The problem.
  • one aspect of the present invention provides a curable resin composition, the curable resin composition comprising a photopolymerization initiator (A), a carboxyl group-containing resin (B) and a photopolymerizable monomer (C),
  • the polymerization initiator (A) includes a first photopolymerization initiator (A1) and a second photopolymerization initiator (A2), wherein the first photopolymerization initiator (A1) is selected from free-radical oxime ester-based photopolymerization initiators , one or more of the group consisting of a radical type imidazole-based photopolymerization initiator, an alkylphenone-based photopolymerization initiator, and an acylphosphine oxide-based photopolymerization initiator, and the second photopolymerization initiator (A2) has The structure shown in general formula (I):
  • two R 1 are each independently selected from hydrogen, C 1 -C 10 straight or branched chain alkyl, or C 2 -C 10 alkenyl, or two R 1 form a cyclic Structure;
  • R 2 and R 3 independently represent C 1 -C 10 straight or branched chain alkyl;
  • R 4 represents a photoactive group;
  • A represents hydrogen, nitro, halogen or -CO-CR 2 R 3 R 4 groups.
  • two R 1 are each independently selected from hydrogen, C 1 -C 6 straight or branched chain alkyl or C 2 -C 6 alkenyl, or two R 1 form Four-membered, five-membered or six-membered ring.
  • R 2 and R 3 independently represent a C 1 -C 6 straight-chain or branched-chain alkyl group.
  • R 4 is hydroxyl or N-morpholinyl.
  • A is hydrogen or a -CO-CR 2 R 3 R 4 group
  • R 2 , R 3 and R 4 in the substituent -CO-CR 2 R 3 R 4 group have the same definitions as described above .
  • the weight ratio of the first photopolymerization initiator (A1) and the second photopolymerization initiator (A2) is (0.5-5):(5-9.5).
  • the curable resin composition further includes a thermosetting component (D), preferably, the thermosetting component (D) is selected from blocked isocyanate compounds, amino resins, maleimide compounds, benzoxazine resins, One or more of the group consisting of carbodiimide resins, cyclic carbonate compounds, multifunctional epoxy compounds, multifunctional oxetane compounds, and episulfide resins.
  • a thermosetting component (D) is selected from blocked isocyanate compounds, amino resins, maleimide compounds, benzoxazine resins, One or more of the group consisting of carbodiimide resins, cyclic carbonate compounds, multifunctional epoxy compounds, multifunctional oxetane compounds, and episulfide resins.
  • Another aspect of the present application also provides a solder mask, which is formed by curing the curable resin composition provided by the present application.
  • Yet another aspect of the present application also provides a printed circuit board, including a solder mask, and the solder mask includes the above-mentioned solder mask.
  • Another aspect of the present application also provides an interlayer insulating material, which is formed by curing the above curable resin composition.
  • the first photopolymerization initiator (A1) and the second photopolymerization initiator (A2) has better photoinitiating activity and stability, and using them as the photopolymerization initiator (A) can
  • the carboxyl group-containing resin (B) and the photopolymerizable monomer (C) are further cured, which is advantageous in improving the heat resistance and adhesiveness of the cured product formed therefrom.
  • the carboxyl group-containing resin (B) enables the curable resin composition to be an alkali-developable curable resin composition, and improves the resolution of the developed pattern.
  • the addition of the photopolymerizable monomer (C) can adjust the chemical resistance and curing rate of the above-mentioned curable composition.
  • the above compositions have excellent curability in both thick coatings and systems with high colorant content, as well as high resolution and good heat resistance, chemical resistance and adhesion. sex.
  • the present application provides a curable resin composition comprising a photopolymerization initiator (A), a carboxyl group-containing resin (B) and a photopolymerizable monomer (C), and the photopolymerization
  • the initiator (A) includes a first photopolymerization initiator (A1) and a second photopolymerization initiator (A2), wherein the first photopolymerization initiator (A1) is selected from the group consisting of free-radical oxime ester-based photopolymerization initiators, One or more of the group consisting of a radical type imidazole-based photopolymerization initiator, an alkylphenone-based photopolymerization initiator, and an acylphosphine oxide-based photopolymerization initiator, and the second photopolymerization initiator (A2) has the following properties: The structure
  • two R 1 are each independently selected from hydrogen, C 1 -C 10 straight or branched chain alkyl, C 2 -C 10 alkenyl, or two R 1 form a cyclic structure ;
  • R 2 and R 3 independently represent a straight-chain or branched alkyl group of C 1 to C 10 ;
  • R 4 represents a photoactive group;
  • A represents hydrogen, nitro, halogen or -CO-CR 2 R 3 R 4 group.
  • first photopolymerization initiator (A1) and the second photopolymerization initiator (A2) has better photoinitiating activity and stability, and using them as the photopolymerization initiator (A) can interact with the carboxyl-containing resin (B) and The photopolymerizable monomer (C) is more deeply cured, and further contributes to improving the heat resistance and the adhesiveness of the cured product formed by the photopolymerizable monomer (C).
  • the carboxyl group-containing resin (B) enables the curable resin composition to be an alkali-developable curable resin composition, and improves the resolution of the developed pattern.
  • the addition of the photopolymerizable monomer (C) can adjust the chemical resistance and curing rate of the above-mentioned curable composition.
  • the above compositions have excellent curability in both thick coatings and systems with high colorant content, as well as high resolution and good heat resistance, chemical resistance and adhesion. sex.
  • the second photopolymerization initiator (A2) has the structure shown in general formula (I):
  • two R 1 independently represent hydrogen, C 1 -C 10 straight or branched chain alkyl or C 2 -C 10 alkenyl, or two R 1 can also be connected to form a ring ;
  • R 2 and R 3 independently of each other represent a C 1 -C 10 straight-chain or branched alkyl group;
  • R 4 represents a photoactive group;
  • A represents hydrogen, nitro, halogen or -CO-CR 2 R 3 R 4 group.
  • two R 1 are independently selected from hydrogen, C 1 -C 6 straight or branched chain alkyl or C 2 -C 6 alkenyl, Or two R 1 form a four-membered ring, a five-membered ring or a six-membered ring.
  • R 2 and R 3 independently represent a C 1 -C 6 straight-chain or branched-chain alkyl group.
  • R 4 is hydroxyl or N-morpholinyl.
  • A is hydrogen or a -CO-CR 2 R 3 R 4 group
  • R 2 , R 3 and R 4 in the substituent -CO-CR 2 R 3 R 4 group are the same as those described above.
  • Corresponding parts have the same definitions.
  • the radical type imidazole-based photopolymerization initiator is a bisimidazole-based photoinitiator; more preferably, the above-mentioned bisimidazole-based photoinitiator includes but is not limited to 2,2'-bis(o-chloro) Phenyl)-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
  • the free-radical oxime ester-based photopolymerization initiator includes, but is not limited to, 1-(4-phenylthiophenyl)-n-octane-1,2-dione-2-benzoic acid Oxime ester, 1-[6-(2-methylbenzoyl)-9-ethylcarbazol-3-yl]-ethan-1-one-acetic oxime ester, 1-[6-(2-methyl ylbenzoyl)-9-ethylcarbazol-3-yl]-butane-1-one-acetoxime ester, 1-[6-(2-methylbenzoyl)-9-ethylcarbazole -3-yl]-propan-1-one-acetic oxime ester, 1-[6-(2-methylbenzoyl)-9-ethylcarbazol-3-yl]-1-cyclohexyl-methane- 1-Keto-acetic oxime ester, 1-[6-[6-(2-
  • the radical-type oxime ester-based photopolymerization initiator may be selected from commercially available CGI-325 manufactured by BASF JAPAN LTD., IRGACUREOXE01, IRGACUREOXE02, N-1919 manufactured by ADEKACORPORATION, and the like.
  • the alkylphenone-based photopolymerization initiators include but are not limited to benzil dimethyl ketal-based photopolymerization initiators, ⁇ -hydroxyalkylphenone-based photopolymerization initiators, ⁇ -hydroxyalkylphenone-based photopolymerization initiators, - One or more of the group consisting of an aminoacetophenone-based photopolymerization initiator and an acylphosphine oxide-based photopolymerization initiator.
  • benzil dimethyl ketal-based photopolymerization initiators include but are not limited to 2,2-dimethoxy-1,2-diphenylethane-1-one; Commercially available products of the ketal-based photopolymerization initiator include IRGACURE651 manufactured by BASF JAPAN LTD., and the like.
  • ⁇ -hydroxyalkylphenone-based photopolymerization initiators include but are not limited to 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1- ketone, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one and 2-hydroxy-1- ⁇ 4-[4-( One or more of the group consisting of 2-hydroxy-2-methyl-propionyl)-benzyl]phenyl ⁇ -2-methyl-propan-1-one; as ⁇ -hydroxyalkylphenone series
  • Commercially available products of the photopolymerization initiator include IRGACURE184, DAROCUR1173, IRGACURE2959, and IRGACURE127 manufactured by BASF JAPAN LTD.
  • ⁇ -aminoacetophenone-based photopolymerization initiators include but are not limited to 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinoacetone-1, 2-benzyl Alkyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl ]-1-[4-(4-morpholinyl)phenyl]-1-butanone, N,N-dimethylaminoacetophenone.
  • Commercially available ⁇ -aminoacetophenone-based photopolymerization initiators include IRGACURE907, IRGACURE369, and IRGACURE379 manufactured by BASF JAPAN LTD.
  • acylphosphine oxide-based photopolymerization initiators include, but are not limited to, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)- Phenylphosphine oxide and/or bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide, etc.
  • acylphosphine oxide type photoinitiator TPO, 819 etc. by BASF JAPAN LTD. are mentioned.
  • the first photopolymerization initiator (A1) is an imidazole-based photoinitiator.
  • the weight percentage of the photopolymerization initiator in the curable resin composition is 2 to 25 wt %, and more It is preferably 2.5 to 10 wt %.
  • the weight ratio of the first photopolymerization initiator (A1) and the second photopolymerization initiator (A2) is (0.5-5):(5-9.5).
  • the carboxyl group-containing resin can make the curable resin composition an alkali-developable curable resin composition, and can obtain high resolution during development.
  • the carboxyl group-containing resin (B) is not particularly limited, and known carboxyl group-containing resins used in curable resin compositions for solder resists and interlayer insulating layers can be employed.
  • the carboxyl group-containing resin preferably has an ethylenically unsaturated bond in addition to the carboxyl group. More preferably, the above-mentioned ethylenically unsaturated double bond is a double bond derived from acrylic acid or methacrylic acid or derivatives thereof. Or when the carboxyl group-containing resin (B) does not have an ethylenically unsaturated bond, in order to improve the photocurability of the curable composition, a compound having one or more ethylenically unsaturated groups in the molecule ( photoreactive monomers).
  • the carboxyl-containing resin containing carboxyl groups in the above-mentioned molecules and not having ethylenically unsaturated bonds in the molecule includes but is not limited to the following:
  • Carboxyl group-containing compounds obtained by copolymerizing unsaturated carboxylic acids such as acrylic acid and methacrylic acid with compounds having unsaturated double bonds such as styrene, ⁇ -methylstyrene, lower alkyl (meth)acrylate, and isobutylene resin;
  • Hydroxyl-containing polymers such as olefin-based hydroxyl-containing polymers, acrylic polyols, rubber-based polyols, polyvinyl acetal, styrene allyl alcohol-based resins, celluloses, etc. are mixed with saturated or unsaturated The carboxyl-containing resin obtained by the reaction of polybasic acid anhydrides;
  • bisphenol A type epoxy resin bisphenol F type epoxy resin, bisphenol S type epoxy resin, brominated bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, biphenol type epoxy resin Reaction products of epoxy resins, bixylenol type epoxy resins and other diepoxy compounds with dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, phthalic acid, isophthalic acid, and saturated or Carboxyl-containing resin obtained by the reaction of unsaturated polybasic acid anhydrides;
  • dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, phthalic acid, isophthalic acid, and saturated or Carboxyl-containing resin obtained by the reaction of unsaturated polybasic acid anhydrides
  • a carboxyl group-containing resin obtained by reacting a bifunctional epoxy compound with bisphenols such as bisphenol A and bisphenol F, and a saturated or unsaturated polybasic acid anhydride.
  • the carboxyl group-containing resin having a carboxyl group in the aforementioned molecule and an ethylenically unsaturated bond in the molecule include but not limited to the following:
  • a polyfunctional epoxy compound having at least two epoxy groups in one molecule such as a novolak-type epoxy resin, is reacted with an unsaturated monocarboxylic acid such as (meth)acrylic acid, and the generated hydroxyl group reacts with hexahydro-o Carboxyl-containing resins obtained by the reaction of saturated or unsaturated polybasic acid anhydrides such as phthalic anhydride and tetrahydrophthalic anhydride;
  • a polyfunctional epoxy compound having at least two epoxy groups in one molecule such as a novolak-type epoxy resin, an unsaturated monocarboxylic acid such as (meth)acrylic acid, and a nonylphenol having in one molecule
  • the carboxyl-containing resin obtained by reacting with saturated or unsaturated polybasic acid anhydrides such as hexahydrophthalic anhydride and tetrahydrophthalic anhydride;
  • Copolymers of unsaturated carboxylic acids such as (meth)acrylic acid and maleic acid, and photopolymerizable monomers such as methyl (meth)acrylate, and glycidyl (meth)acrylate, etc. have in one molecule A carboxyl-containing resin obtained by the reaction of one epoxy group with a compound with an ethylenically unsaturated double bond, and the resulting hydroxyl group reacted with saturated or unsaturated polybasic acid anhydrides such as hexahydrophthalic anhydride and tetrahydrophthalic anhydride ;
  • Copolymers of unsaturated dibasic acid anhydrides such as maleic anhydride and photopolymerizable monomers such as methyl (meth)acrylate, and hydroxy (meth)acrylates such as 2-hydroxyethyl (meth)acrylate A carboxyl group-containing resin obtained by reacting an alkyl ester, etc.
  • the polyfunctional epoxy compound used in the synthesis of the above-mentioned resin has a bisphenol A structure, a bisphenol F structure, a biphenol structure, a biphenol novolak structure, a bixylenol structure, and particularly has a biphenyl novolak structure.
  • the cured product of the curable resin composition obtained is preferable because of low warpage and excellent bending resistance.
  • (meth)acrylate here is a term collectively referring to acrylate, methacrylate, and a mixture thereof, and the same applies to other similar expressions below.
  • the acid value of the said carboxyl group containing resin becomes like this.
  • it is the range of 20-200 mgKOH/g, More preferably, it is the range of 40-150 mgKOH/g.
  • the acid value of the carboxyl group-containing resin is 20 mgKOH/g or more, the adhesiveness of the coating film can be obtained, and when a curable resin composition is formed, the alkali developability is favorable.
  • the acid value is 200 mgKOH/g or less, the dissolution of the exposed part by the developing solution can be suppressed, and the lines are not made thinner than necessary, and the exposed part and the unexposed part can be suppressed from being exposed to the developing solution without distinction. It dissolves and peels off, so that it becomes easy to draw a normal resist pattern.
  • the weight-average molecular weight of the above-mentioned carboxyl group-containing resin varies depending on the resin skeleton, and preferably, the weight-average molecular weight of the carboxyl group-containing resin is 2,000 to 150,000.
  • the weight average molecular weight is 2000 or more, the non-stick performance is excellent, the moisture resistance of the coating film after exposure is good, the film reduction does not occur during development, and the resolution is good.
  • the weight average molecular weight is 150,000 or less, the developability is good and the storage stability is also excellent. More preferably, the weight average molecular weight of the carboxyl group-containing resin is 5,000-100,000.
  • the photopolymerizable monomer is a compound that insolubilizes the carboxyl group-containing resin or contributes to insolubilization in an alkaline aqueous solution after photocuring by irradiation with active energy rays, and the photopolymerizable monomer (C) can also be used as a curable It is used as a diluent for the resin composition.
  • photopolymerizable monomers those commonly used in this field can be used.
  • (meth)acrylic acid 2-ethylhexyl ester, (meth)acrylic acid cyclohexyl ester and other (meth)acrylic acid alkyl ester organic compounds (meth)acrylic acid 2-hydroxyethyl, (meth)acrylic acid 2 -Hydroxyalkyl (meth)acrylate organic compounds such as hydroxypropyl; mono- or di(meth)acrylate organic compounds of alkylene oxide derivatives such as ethylene glycol, propylene glycol, diethylene glycol, and dipropylene glycol; hexanediol Alcohols, trimethylolpropane, pentaerythritol, bis(trimethylolpropane), bis(pentaerythritol), trimethylolisocyanurate and other polyhydric alcohols or their ethylene oxide or propylene oxide ad
  • the said photopolymerizable monomer (C) may be used individually by 1 type, and may be used in combination of 2 or more types.
  • the compounding quantity of the said photopolymerizable monomer (C) is solid content conversion,
  • the weight percentage content of the photopolymerizable monomer (C) in a curable resin composition is 1-30 wt%. If it is 30 weight% or less, the surface does not become sticky, and touch-drying property is favorable. Moreover, when it is 1 weight% or more, sufficient photocurability can be acquired at the time of exposure, and pattern formability is favorable.
  • the weight percentage of the photopolymerizable monomer (C) is 2-20 wt %, more preferably 5-15 wt %.
  • the curable resin composition preferably further includes a thermosetting component (D).
  • the thermosetting component (D) includes but is not limited to blocked isocyanate compounds, amino resins, maleimide compounds, benzoxazine resins, carbodiimide resins, cyclic carbonates One or more of the group consisting of compounds, polyfunctional epoxy compounds, polyfunctional oxetane compounds, and episulfide resins.
  • the above-mentioned multifunctional epoxy compounds include but are not limited to epoxidized vegetable oil, bisphenol A epoxy resin, hydroquinone epoxy resin, bisphenol epoxy resin, and thioether ring Oxygen resin, brominated epoxy resin, novolak type epoxy resin, biphenol novolak type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, glycidylamine type epoxy resin, Hydantoin type epoxy resin, alicyclic epoxy resin, trihydroxyphenylmethane type epoxy resin, bisphenol S type epoxy resin, bisphenol A novolac type epoxy resin, tetraphenolethane type epoxy resin Oxygen resin, heterocyclic epoxy resin, diglycidyl phthalate resin, tetraglycidyl xylenol ethane resin, naphthyl-containing epoxy resin, epoxy resin having a dicyclopentadiene skeleton, methyl alcohol glycidyl acrylate copolymer epoxy resin, cyclo
  • the multifunctional oxetane compounds include, but are not limited to, multifunctional oxetane compounds, etherates of resins with hydroxyl groups, and unsaturated mono-unsaturated oxetane rings.
  • polyfunctional oxetanes include, but are not limited to, bis[(3-methyl-3-oxetanylmethoxy)methyl]ether, bis[(3-ethyl-3 -Oxetanylmethoxy)methyl]ether, 1,4-bis[(3-methyl-3-oxetanylmethoxy)methyl]benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy)methyl]benzene, (3-methyl-3-oxetanyl)methyl acrylate, (3-ethyl- 3-oxetanyl) methyl ester, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl methacrylate) ) methyl esters, or one or more of the group consisting of their oligomers or copolymers.
  • etherates of resins with hydroxyl groups include, but are not limited to, oxetanol, novolac resins, poly(p-hydroxystyrene), cardo-type bisphenols, calixarenes, resorcinol calix Aromatic compounds, or silsesquioxane.
  • Episulfide resins having a plurality of cyclic sulfide groups include, but are not limited to, YL7000 (bisphenol A type episulfide resin) manufactured by Mitsubishi Chemical Corporation, YSLV-120TE manufactured by Todo Chemical Co., Ltd., and the like.
  • episulfide resins etc. in which the oxygen atoms of the epoxy groups of the novolak-type epoxy resins are replaced with sulfur atoms can also be used in the same synthesis method.
  • Examples of commercially available epoxy resins include jER828, 806, 807, YX-8000, 8034, and jER834 manufactured by Mitsubishi Chemical Corporation, and YD-128, YDF-170, and ZX- 1059, ST-3000, 830, 835, 840, 850, N-730A, N695 manufactured by DIC Corporation and RE-306 manufactured by Nippon Kayaku Corporation.
  • the curable resin composition of the present invention further includes a thermosetting catalyst in addition to the above-mentioned thermosetting resin components.
  • a thermosetting catalyst in addition to the above-mentioned thermosetting resin components.
  • Any compound that can achieve the above-mentioned object can be used as a thermal curing catalyst.
  • the above-mentioned thermally curable catalyst includes, but is not limited to, one or more of the group consisting of imidazole derivatives, amine compounds, hydrazine compounds, organic phosphines, melamines, guanamine compounds and s-triazine compounds .
  • imidazole derivatives include but are not limited to imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl - One or more of the group consisting of 2-phenylimidazole and 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole; amine compounds include but are not limited to dicyandiamide, benzyl Dimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine and 4-methyl-N,N- One or more of the group consisting of dimethylbenzylamine; hydrazine compounds including but not limited to adipic acid dihydrazide and/or sebacic acid dihydrazide; organophosphorus including but not limited to triphenylphosphine
  • Guanamine compounds include, but are not limited to, guanamine and/or benzoguanamine).
  • S-triazine derivatives include but are not limited to 2,4-diamino-6-methyl-1,3,5-triazine, 2,4-diamino-6-methacryloyloxyethyl-s-triazine oxazine, 2-vinyl-2,4-diamino-s-triazine, 2-vinyl-4,6-diamino-s-triazine-isocyanuric acid adduct, 2,4-diamino-6 - One or more of the group consisting of methacryloyloxyethyl-s-triazine ⁇ isocyanuric acid adducts.
  • the curable resin composition further includes additives, more preferably, the additives are selected from thermal polymerization inhibitors, ultraviolet absorbers, silane coupling agents, plasticizers, Burning agent, antistatic agent, antiaging agent, antibacterial/antifungal agent, antifoaming agent, leveling agent, filler, thickener, adhesion imparting agent, thixotropy imparting agent, colorant, sensitizer, supply One or more of the group consisting of hydrogen and solvent.
  • the additives are selected from thermal polymerization inhibitors, ultraviolet absorbers, silane coupling agents, plasticizers, Burning agent, antistatic agent, antiaging agent, antibacterial/antifungal agent, antifoaming agent, leveling agent, filler, thickener, adhesion imparting agent, thixotropy imparting agent, colorant, sensitizer, supply One or more of the group consisting of hydrogen and solvent.
  • the curable resin composition of the present invention may contain a filler (inorganic filler).
  • the filler is used in order to suppress curing shrinkage of the cured product of the curable resin composition and to improve characteristics such as adhesiveness and hardness.
  • examples of fillers include barium sulfate, amorphous silica, fused silica, spherical silica, talc, clay, magnesium carbonate, calcium carbonate, alumina, aluminum hydroxide, silicon nitride, aluminum nitride, boron nitride, Noyburg Silica, etc.
  • the average particle diameter (D50) of the filler is preferably 1 ⁇ m or less, more preferably 0.7 ⁇ m or less, and further preferably 0.5 ⁇ m or less.
  • the average particle diameter (D50) can be measured by a laser diffraction/scattering method. When the average particle diameter is in the above-mentioned range, the refractive index becomes close to the resin component, and the transmittance improves.
  • an organic solvent a well-known thing can be used.
  • an organic solvent may be used individually by 1 type, and may be used in mixture of 2 or more types.
  • the organic solvent includes but is not limited to one or more of the following: ketone solvents such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbon solvents such as toluene, xylene, tetratoluene; cellosolve, methyl cellosolve, Butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, diethylene glycol monomethyl ether acetate, tripropylene glycol monomethyl ether Methyl ether and other glycol ether solvents; ethyl acetate, butyl acetate, butyl lactate, cellosolve acetate
  • the organic solvent is generally used for the purpose of preparing a composition, forming a dry film, adjusting the viscosity at the time of coating on a printed circuit board, and the like. Therefore, content of an organic solvent can be suitably changed according to the objective.
  • the sensitizers can include (but are not limited to): anthracene photoinitiators, coumarin photoinitiators, thioxanthone photoinitiators, acridine photoinitiators and other photoinitiators known to those skilled in the art initiator.
  • the anthracene 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(methyl 4-chlorobutyrate), 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-phenylanthr
  • the coumarin compounds include but are not limited to: 3,3'-carbonylbis(7-diethylamine coumarin), 3-benzoyl-7-diethylamine coumarin 3,3'-carbonylbis(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 may be used alone or in combination of two or more.
  • the thioxanthone compounds include but are not limited to: thioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-dithioxanthone Isopropyl thioxanthone, 2-chlorothioxanthone, 1-chloro-4-propoxythioxanthone, isopropyl thioxanthone, diisopropyl thioxanthone.
  • acridine compounds include but are not limited to: 9-phenyl acridine, 9-p-methylphenyl acridine, 9-m-methyl phenyl acridine, 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.
  • the above sensitizers can be used alone or in combination.
  • the weight percentage of the sensitizers is 0.01-10 wt%, preferably 0.01-5 wt%.
  • the content of the sensitizer includes, but is not limited to, the above range, and it is beneficial to further improve the sensitivity of the curable resin composition if it is limited to the above range.
  • the curable resin composition of the present invention is characterized in that the combination of a specific photoinitiator can improve the curing performance of the composition, and it is particularly preferable to use an imidazole compound in combination with the compound of the general formula (I).
  • the curable composition in order to improve the sensitivity, preferably further includes a hydrogen donor. Biimidazole compounds are cracked by light, and the monoimidazole free radicals produced are larger in size, and the steric hindrance effect makes the activity less, so it is difficult to initiate the polymerization of monomers alone. The active hydrogen on the hydrogen donor body is captured, new active free radicals are generated, and the monomer polymerization is initiated.
  • Amine compounds are not particularly limited, and may include (but are not limited to): aliphatic amine compounds, such as triethanolamine, methyldiethanolamine, triisopropanolamine, etc.; aromatic amine compounds, such as methyl 4-dimethylaminobenzoate Ester, Ethyl 4-Dimethylaminobenzoate, Isoamyl 4-Dimethylaminobenzoate, 2-Ethylhexyl 4-Dimethylaminobenzoate, 2-Dimethylaminoethylbenzoate, N , N-dimethyl-p-toluidine, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, etc.
  • aliphatic amine compounds such as triethanolamine, methyldiethanolamine, triisopropanolamine, etc.
  • aromatic amine compounds such as methyl 4-dimethylaminobenzoate Ester, Ethy
  • Carboxylic acid compounds are not particularly limited, and can include (but are not limited to): aromatic heteroacetic acid, phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid Acetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenyl Glycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid, etc.
  • the organosulfur compounds containing mercapto groups are not particularly limited, and may include (but are not limited to): 2-mercaptobenzothiazole (MBO), 2-mercaptobenzimidazole (MBI), dodecyl mercaptan, ethylene glycol bis( 3-mercaptobutyrate), 1,2-propanediol bis(3-mercaptobutyrate), diethylene glycol bis(3-mercaptobutyrate), butanediol bis(3-mercaptobutyrate), Octanediol bis(3-mercaptobutyrate), Trimethylolpropane tris(3-mercaptobutyrate), Pentaerythritol tetrakis(3-mercaptobutyrate), Dipentaerythritol hexa(3-mercaptobutyrate) , ethylene glycol bis(2-mercaptopropionate), propylene glycol bis(2-mercaptopropionate), diethylene glycol
  • Alcohol compounds are not particularly limited, and may include (but are not limited to): methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, neopentanol, n-hexanol, cyclohexanol, Ethylene glycol, 1,2-propanediol, 1,2,3-propanetriol, benzyl alcohol, phenethyl alcohol, etc.
  • the weight percentage of the hydrogen donor is 0.01-20 wt %, preferably 0.01-10 wt %.
  • the content of the hydrogen donor is within the above range, it is advantageous to adjust the sensitivity of the curable resin composition.
  • the curable resin composition of this invention can mix
  • a coloring agent known colorants such as red, blue, green, and yellow can be used, and any of pigments, dyes, and dyes may be used. Specifically, those with the following Dye Index (C.I.; issued by The Society of Dyers and Colourists) number can be cited. Among them, it is preferable to not contain halogen from the viewpoint of reducing the environmental load and the influence on the human body.
  • red colorants there are monoazo-based, disazo-based, azo-lake-based, benzimidazolone-based, perylene-based, diketopyrrolopyrrole-based, condensed azo-based, anthraquinone-based, quinacridine-based colorants
  • pyridone series specifically, the following can be exemplified.
  • Monoazo series Pigment Red 1, 2, 3, 4, 5, 6, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 112, 114, 146, 147 , 151, 170, 184, 187, 188, 193, 210, 245, 253, 258, 266, 267, 268, 269.
  • Disazo series Pigment Red 37, 38, 41.
  • Monoazo Lake Series Pigment Red 48:1, 48:2, 48:3, 48:4, 49:1, 49:2, 50:1, 52:1, 52:2, 53:1, 53 :2, 57:1, 58:4, 63:1, 63:2, 64:1, 68.
  • Benzimidazolone series Pigment Red 171, Pigment Red 175, Pigment Red 176, Pigment Red 185, Pigment Red 208.
  • Diketopyrrolopyrrole series Pigment Red 254, Pigment Red 255, Pigment Red 264, Pigment Red 270, Pigment Red 272.
  • Condensed azo series Pigment Red 220, Pigment Red 144, Pigment Red 166, Pigment Red 214, Pigment Red 220, Pigment Red 221, Pigment Red 242.
  • Anthraquinone series Pigment Red 168, Pigment Red 177, Pigment Red 216, Solvent Red 149, Solvent Red 150, Solvent Red 52, Solvent Red 207.
  • blue colorants include phthalocyanine-based and anthraquinone-based colorants.
  • Pigment-based colorants are compounds classified as pigments, and specific examples include the following: Pigment Blue 15, Pigment Blue 15:1, Pigment Blue 15:2 , Pigment Blue 15:3, Pigment Blue 15:4, Pigment Blue 15:6, Pigment Blue 16, Pigment Blue 60.
  • Solvent Blue 35 Solvent Blue 63, Solvent Blue 68, Solvent Blue 70, Solvent Blue 83, Solvent Blue 87, Solvent Blue 94, Solvent Blue 97, Solvent Blue 122, Solvent Blue 136, Solvent Blue 67, Solvent Blue 70, etc.
  • metal-substituted or unsubstituted phthalocyanine compounds can also be used.
  • the green colorant there are also phthalocyanine-based, anthraquinone-based, and perylene-based colorants. Specifically, Pigment Green 7, Pigment Green 36, Solvent Green 3, Solvent Green 5, Solvent Green 20, Solvent Green 28, and the like can be used. In addition to the above, metal-substituted or unsubstituted phthalocyanine compounds can also be used.
  • the yellow colorant there are monoazo-based, disazo-based, condensed azo-based, benzimidazolone-based, isoindolinone-based, anthraquinone-based, and the like, and specifically, the following are exemplified.
  • Anthraquinone series Solvent Yellow 163, Pigment Yellow 24, Pigment Yellow 108, Pigment Yellow 193, Pigment Yellow 147, Pigment Yellow 199, Pigment Yellow 202.
  • Isoindolinone series Pigment Yellow 110, Pigment Yellow 109, Pigment Yellow 139, Pigment Yellow 179, Pigment Yellow 185.
  • Condensed azo series Pigment Yellow 93, Pigment Yellow 94, Pigment Yellow 95, Pigment Yellow 128, Pigment Yellow 155, Pigment Yellow 166, Pigment Yellow 180.
  • Benzimidazolone series Pigment Yellow 120, Pigment Yellow 151, Pigment Yellow 154, Pigment Yellow 156, Pigment Yellow 175, Pigment Yellow 181.
  • Monoazo series Pigment Yellow 1, 2, 3, 4, 5, 6, 9, 10, 12, 61, 62, 62:1, 65, 73, 74, 75, 97, 100, 104, 105, 111 , 116, 167, 168, 169, 182, 183.
  • Disazo series Pigment Yellow 12, 13, 14, 16, 17, 55, 63, 81, 83, 87, 126, 127, 152, 170, 172, 174, 176, 188, 198.
  • colorants such as purple, orange, brown, black, etc. may be added.
  • the colorant can be properly compounded.
  • the weight ratio of the carboxyl group-containing resin (B) or the thermosetting component (D) to the colorant is greater than 100:10, more preferably 100:10. 100: (0.1 to 5).
  • the curable resin composition of the present invention may be used as a dry film, or may be used as it is in a liquid state. When used in a liquid form, it may be one-component or two-component or more.
  • the curable resin composition of this invention can be used for forming the pattern layer of the permanent film of the printed wiring board, such as a solder resist layer, a cover layer, an interlayer insulating layer, etc., and it is especially useful for forming a solder resist layer.
  • the curable resin composition of the present invention can also be suitably used for printed wiring boards requiring thinning, such as IC package substrates (printed boards used in IC packages). The formation of pattern layers in circuit boards).
  • the cured product obtained from the curable resin composition of the present invention has the advantages of high elastic modulus and low CTE (coefficient of expansion), and thus can be suitably used for forming a pattern layer in an IC package substrate having a thin overall thickness and insufficient rigidity.
  • the curable resin composition of the present invention may be in the form of a dry film including a carrier film (support) and a resin layer formed of the curable resin composition described above formed on the carrier film.
  • the curable resin composition of the present invention is diluted with the above-mentioned organic solvent to adjust to an appropriate viscosity, and is passed through a comma coater, a knife coater, and a lip coater. coater), rod coater, squeeze coater, reverse coater, transfer rollcater, gravure coater or
  • the spraying machine coats the carrier film to a uniform thickness, and usually the film is obtained by drying at a temperature of 50 to 130° C. for 1 to 30 minutes.
  • the coating film thickness is not particularly limited, but is usually appropriately selected within the range of 1 to 150 ⁇ m, preferably 10 to 60 ⁇ m, in terms of the film thickness after drying.
  • a plastic film can be used, and preferably a polyester film such as polyethylene terephthalate, a polyimide film, a polyamideimide film, a polypropylene film, or a polystyrene film or the like is used.
  • the thickness of the carrier film is not particularly limited, and is usually appropriately selected within the range of 10 to 150 ⁇ m.
  • the peelable cover film for example, polyethylene film, polytetrafluoroethylene film, polypropylene film, surface-treated paper, etc. can be used, as long as the adhesive force between the resin layer and the cover film is smaller than that between the resin layer and the cover film when the cover film is peeled off. The adhesive force of the carrier film is sufficient.
  • the printed wiring board of the present invention has a cured product obtained from the curable resin composition of the present invention or the resin layer of the dry film.
  • the curable resin composition of the present invention is adjusted to a viscosity suitable for a coating method using the above-mentioned organic solvent, and a dip coating method, a flow coating method, a roll coating method, a bar coating method, Coating method, screen printing method or curtain coating method, etc. are applied to the substrate, and then the organic solvent contained in the composition is volatilized and dried (temporarily dried) at a temperature of 60 to 100 ° C to form a non-stick resin layer.
  • the resin layer is formed on the base material by bonding the resin layer to the base material using a laminator or the like so that the resin layer is in contact with the base material, and then peeling off the carrier film.
  • the base material in addition to printed wiring boards and flexible printed wiring boards in which circuits are previously formed by copper or the like, paper-phenol resin, paper-epoxy resin, glass cloth-epoxy resin, glass- Polyimide, glass cloth/non-woven fabric - epoxy resin, glass cloth/paper - epoxy resin, synthetic fiber - epoxy resin, fluororesin, polyethylene, polyphenylene oxide (polyphenylene oxide) All grades (FR-4, etc.) of copper clad laminates for high frequency circuits such as cyanate esters and other materials, as well as metal substrates, polyimide films, PET films, polyethylene naphthalate Ester (PEN) film, glass substrate, ceramic substrate, wafer plate, etc.
  • cyanate esters and other materials such as well as metal substrates, polyimide films, PET films, polyethylene naphthalate Ester (PEN) film, glass substrate, ceramic substrate, wafer plate, etc.
  • a hot air circulation drying furnace for volatilization drying after applying the curable resin composition of the present invention, a hot air circulation drying furnace, an IR furnace, a hot plate, a convection oven, or the like can be used (a device having a heat source of an air heating method using steam is used, and the inside of the dryer is allowed to dry.
  • the method of hot air convective contact and the method of blowing to the support through a nozzle) are carried out.
  • the resin layer is formed on the substrate, it is selectively exposed with active energy rays through a photomask having a predetermined pattern, and the unexposed portion is developed with a dilute alkaline aqueous solution (for example, a 0.3 to 3 wt % sodium carbonate aqueous solution).
  • a pattern of the cured product is formed.
  • the cured product is irradiated with active energy rays and then heated and cured (for example, 100 to 220° C.), or heated and cured, and then irradiated with active energy rays, or only heated and cured to be finally cured (complete curing), thereby forming Cured film excellent in various properties such as adhesion and hardness.
  • the exposure machine used for the above-mentioned active energy ray irradiation may be any device that mounts a high-pressure mercury lamp, an LED light source, an ultra-high-pressure mercury lamp, a metal halide lamp, a mercury short-arc lamp, or the like, and irradiates ultraviolet rays in the range of 350 to 450 nm.
  • a direct drawing device eg, a laser direct imaging device that directly draws an image with a laser using CAD data from a computer
  • the maximum wavelength may be in the range of 350 to 410 nm.
  • the exposure amount for forming an image varies depending on the film thickness and the like, but is usually within a range of 10 to 1000 mJ/cm 2 , preferably 20 to 800 mJ/cm 2 .
  • a dipping method, a rinsing method, a spraying method, a brushing method, etc. can be used, and as the developing solution, potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, etc. can be used , amines and other alkaline aqueous solutions.
  • the curable resin composition of the present invention can be used not only for applications in which a pattern of a cured film is formed by the above-mentioned developer, but also in applications in which no pattern is formed, for example, mold applications (sealing applications).
  • solder mask which is formed by curing the curable resin composition provided by the present application.
  • the above compositions have excellent curability in both thick coatings and high colorant content systems, together with high resolution and good heat, chemical and adhesion properties. Therefore, the solder resist film prepared by using it has excellent heat resistance, chemical resistance, adhesion and high resolution.
  • Yet another aspect of the present application also provides a printed circuit board including a solder mask, the solder mask including the solder mask provided by the present application. Because the solder resist film provided by the present application has excellent heat resistance, chemical resistance, adhesion and high resolution. Therefore, the above-mentioned solder resist film is arranged on the printed circuit board, which greatly improves the appearance of the printed circuit board and reduces the amount of colorant.
  • Another aspect of the present application also provides an interlayer insulating material, which is formed by curing the curable resin composition provided by the present application.
  • the above compositions have excellent curability both in thick coatings and in systems with high colorant content, and at the same time have high resolution and good heat resistance, chemical resistance and adhesion. Therefore, the interlayer insulating material prepared by using it has excellent heat resistance, chemical resistance, adhesion and high resolution.
  • each component was premixed with a mixer, and then kneaded with a three-roll mill to prepare a curable resin composition.
  • the photopolymerization initiator in the comparative example adopts 2-methyl-1-(4-methylthiophenyl)-2-morpholine-1-acetone, which is commonly used in the current technology, as a comparison.
  • the present invention will be further specifically described with reference to Comparative Examples, but the present invention is not limited to the following Examples.
  • the curable resin compositions of Examples and Comparative Examples were applied on a copper-filled substrate at a thickness of about 25 ⁇ m by screen printing, and dried in a hot air circulating drying oven at 80° C. for 30 minutes. After drying, the substrate was left to reach room temperature, and then exposed in stages at 200 mj/cm 2 with a 150 mj/cm 2 and a 405 nm LED exposure machine (RW-UVAP202-20gl) using an exposure device (ELS106SA) equipped with a metal halide lamp, respectively.
  • ELS106SA exposure device equipped with a metal halide lamp
  • the dried coating film was exposed to light with a meter (Stuffer 21 grade), and the pattern of the stepwise exposure meter remaining after development (1 wt % Na 2 CO 3 aqueous solution, 30° C., 0.2 MPa) for 60 s was read.
  • composition of each said Example and the comparative example was apply
  • the curable resin composition was exposed to light at an optimum exposure amount of 150 mj/cm 2 , and then thermally cured at 150° C. ⁇ 60 min to obtain a cured coating film. Visually observe the appearance of the cured coating;
  • the curable resin compositions of the aforementioned Examples and Comparative Examples were applied on the entire surface of a copper-filled substrate by screen printing so that the film thickness after drying was 25 ⁇ m, and dried at 80° C. for 30 minutes. After the dried substrate was left to reach room temperature, the substrate was subjected to 150 mJ/ cm 2 exposure, 1 wt % sodium carbonate aqueous solution at 30° C. was used for 60 s development under the condition of a spray pressure of 0.2 MPa, and a resist pattern for resolution evaluation was obtained.
  • the curable resin compositions of the aforementioned Examples and Comparative Examples were applied over the entire surface of the patterned copper foil substrate by screen printing, dried at 80° C. for 30 min, and naturally cooled to room temperature.
  • the curable resin composition was exposed at an optimum exposure amount of 150 mj/cm 2 , and developed with a 1 wt % sodium carbonate aqueous solution at 30° C. for 60 s under the condition of a spray pressure of 0.2 MPa to obtain a resist pattern.
  • substrate was heated and hardened at 130 degreeC for 60 minutes, and it was set as the board
  • the cured paint film is coated with rosin-type flux and immersed in a lead-tin furnace at 288°C for 30s. Scrub the surface with butyl glycol ether, and pull 3M tape (model 610#) three times. If there is no oil drop, it means heat resistance is OK, otherwise NG.
  • the evaluation substrate was immersed in a 10 vol% H 2 SO 4 aqueous solution at room temperature for 20 minutes, and the impregnation, the elution of the coating film, and further the peeling due to tape peeling were confirmed visually.
  • the evaluation substrate was immersed in a 10 vol% NaOH aqueous solution at room temperature for 20 minutes, and the impregnation, the elution of the coating film, and the peeling due to tape peeling were confirmed visually.
  • the evaluation substrate was immersed in propylene glycol monomethyl ether at room temperature for 20 minutes, and the impregnation, the elution of the coating film, and the peeling due to tape peeling were confirmed visually.
  • the curable resin compositions of the examples and comparative examples were coated on the full copper substrate and the polyimide polished by the grinding machine at a thickness of about 25 ⁇ m by the screen printing method, in a hot air circulating drying oven at 80 ° C. Dry for 30 minutes. After the dried substrate was left to reach room temperature, the curable resin composition was exposed at an optimum exposure amount of 150 mj/cm 2 , and then thermally cured at 150° C. ⁇ 60 min to obtain a cured coating film.
  • the adhesion test is carried out.
  • the test method is: use a hundred-grid knife, the width of the knife edge is about 10mm ⁇ 12mm, every 1mm ⁇ 1.2mm is an interval, a total of 10
  • 10 straight line knife marks with the same interval will appear.
  • the straight line knife mark is drawn at the vertical position, it will become a 10 ⁇ 10 square of 100 squares. Only cut on the coating, otherwise the test will not hold.
  • the Transparent Tape 600 tape produced by 3M company to test whether it will fall off. First, stick the tape to the 100 grid position, press down with your fingers to stick the tape tightly, and then tear the tape with an instant force. From then on, check whether the paint on the material is peeling off.
  • Grade 0 The edges of the cut are completely smooth, and the edges of the lattice do not have any flaking.
  • Grade 1 Small pieces are peeled off at the intersection of the incision, and the actual damage in the cross-cut area is less than or equal to 5%.
  • Grade 2 The edges and/or intersections of the incision are peeled off, and the area is greater than 5% to 15%.
  • Level 3 Partial peeling or whole large piece peeling off along the edge of the incision, or part of the grid is peeled off in the whole piece, and the peeling area exceeds 15% to 35%.
  • Grade 4 The edge of the incision is largely peeled off/or some squares are partially or completely peeled off, and the area is greater than 35% to 65% of the cutout area.
  • Level 5 There are pieces of paint peeling off at the edges and intersections of the scribed lines, and the total peeling area is greater than 65%.
  • the first photoinitiator of bisimidazole, the first photoinitiator of oxime ester, the first photoinitiator of alkylphenone, and the first photoinitiator of acylphosphine oxide Any one of the polymerization initiators is specifically combined with the second photopolymerization initiator represented by the general formula (I), especially the embodiment of the combination of the bisimidazole-based photoinitiator and the general formula (I).
  • the curable resin composition is excellent in curability and excellent in other comprehensive properties.

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Abstract

一种固化性树脂组合物、及其形成的阻焊膜、层间绝缘材料和印刷电路板。固化性树脂组合物包括光聚合引发剂(A)、含羧基树脂(B)和光聚合性单体(C)，光聚合引发剂(A)包括第一光聚合引发剂(A1)和第二光聚合引发剂(A2)，其中，第一光聚合引发剂(A1)选自自由基型肟酯系光聚合引发剂、自由基型咪唑系光聚合引发剂、烷基苯酮系光聚合引发剂和酰基氧化膦系光聚合引发剂组成的组中的一种或几种，第二光聚合引发剂(A2)具有如通式(I)所示的结构。固化性树脂组合物无论在厚涂层还是在着色剂含量较高的体系中均具有优异的固化性，同时还具有高的分辨率和较好的耐热性、耐化性以及密着性。

Description

固化性树脂组合物、及其形成的阻焊膜、层间绝缘材料和印刷电路板 技术领域
本发明涉及光固化领域，具体而言，涉及一种固化性树脂组合物、及其形成的阻焊膜、层间绝缘材料和印刷电路板。
背景技术
印刷电路板在基材上形成有导体电路图案，在导体电路的焊盘部通过焊接搭载有电子部件，在焊盘部以外的电路部分被覆有阻焊膜，以对导体进行保护。印刷电路板制造过程中所用的阻焊膜不仅可以在焊接工序时保护无关的配线，而且还可作为镀覆处理时的镀覆保护层使用。因此阻焊膜需要具备焊接时的耐热性、镀覆处理时的耐化学药品性、焊接后的绝缘可靠性等优点。另外，阻焊膜还可以降低铜电路因热、湿气或电、损伤、污垢等导致其外观不良的风险。同时为了解决上述问题，通常在阻焊膜中添加着色剂，并提高其浓度，从而让使用者难以看到外观上的不良。但随着着色剂浓度的增加，所带来的不良问题是固化不充分，底干较难。
另一方面，为了降低电力损耗和运转成本，通常使用UV-LED灯代替传统的UV灯作为固化光源。然而，由于UV-LED光为长波长，固化性能低，与目前的UV灯相比，无法充分地使固化性树脂组合物固化，这就需要进一步改善固化性树脂组合物的固化性。同时由于在基材上形成有铜电路，对其涂布阻焊剂或者层压阻焊剂的情况下，其抗蚀膜厚的分布规律为在基材上厚、在铜电路上薄、在铜电路的边缘的部分更薄。在面临上述阻焊膜的厚度不同的状况中，使用UV-LED光源固化时，无法充分固化的缺陷会显得更加明显。
发明内容
本发明的主要目的在于提供一种固化性树脂组合物、及其形成的阻焊膜、层间绝缘材料和印刷电路板，以解决现有的固化性组合物在UV-LED光源下无法充分固化的问题。
为了实现上述目的，本发明一方面提供了一种固化性树脂组合物，该固化性树脂组合物包括光聚合引发剂(A)、含羧基树脂(B)和光聚合性单体(C)，光聚合引发剂(A)包括第一光聚合引发剂(A1)和第二光聚合引发剂(A2)，其中，第一光聚合引发剂(A1)选自自由基型肟酯系光聚合引发剂、自由基型咪唑系光聚合引发剂、烷基苯酮系光聚合引发剂和酰基氧化膦系光聚合引发剂组成的组中的一种或几种，第二光聚合引发剂(A2)具有如通式(I)所示的结构：
Figure PCTCN2021124164-appb-000001
式(I)中，两个R 1各自独立地选自氢、C 1～C 10的直链或支链烷基、或C 2～C 10的链烯基，或两个R 1形成环状结构；R 2和R 3相互独立地表示C 1～C 10的直链或支链烷基；R 4表示光活性基团；A表示氢、硝基、卤素或-CO-CR 2R 3R 4基团。
进一步地，式(I)中，两个R 1各自独立地选自氢、C 1～C 6的直链或支链烷基或C 2～C 6的链烯基，或两个R 1形成四元环、五元环或六元环。
进一步地，式(I)中，R 2和R 3相互独立地表示C 1-C 6的直链或支链烷基。
进一步地，式(I)中，R 4为羟基或N-吗啉基。
进一步地，A为氢或-CO-CR 2R 3R 4基团，且取代基-CO-CR 2R 3R 4基团中的R 2、R 3和R 4与前述内容具有相同的定义。
进一步地，第一光聚合引发剂(A1)和第二光聚合引发剂(A2)的重量比为(0.5～5)：(5～9.5)。
进一步地，固化性树脂组合物还包括热固化性成分(D)，优选地，热固化性成分(D)选自封端异氰酸酯化合物、氨基树脂、马来酰亚胺化合物、苯并噁嗪树脂、碳二亚胺树脂、环碳酸酯化合物、多官能环氧化合物、多官能氧杂环丁烷化合物和环硫树脂组成的组中的一种或多种。
本申请的另一方面还提供了一种阻焊膜，阻焊膜采用本申请提供的固化性树脂组合物固化形成。
本申请的又一方面还提供了一种印刷电路板，包括阻焊膜，阻焊膜包括上述阻焊膜。
本申请的又一方面还提供了一种层间绝缘材料，该层间绝缘材料采用上述固化性树脂组合物固化形成。
应用本发明的技术方案，采用第一光聚合引发剂(A1)和第二光聚合引发剂(A2)具有更好的光引发活性和稳定性，将其作为光聚合引发剂(A)能够和含羧基树脂(B)及光聚合性单体(C)进行更深程度的固化，进而有利于提高其形成的固化物的耐热性和密着性。含羧基树脂(B)能使固化性树脂组合物成为可碱显影的固化性树脂组合物，并提高其显影图案的分辨率。光聚合性单体(C)的加入可以调整上述固化性组合物的耐化性能和固化速率。在此基础上，上述组合物无论在厚涂层还是在着色剂含量较高的体系中均具有优异的固化性，同时还具有高的分辨率和较好的耐热性、耐化性以及密着性。
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。
正如背景技术所描述的，现有的固化性组合物在UV-LED光源下无法充分固化的问题。为了解决上述技术问题，本申请提供了一种固化性树脂组合物，该固化性树脂组合物包括光聚合引发剂(A)、含羧基树脂(B)和光聚合性单体(C)，光聚合引发剂(A)包括第一光聚合引发剂(A1)和第二光聚合引发剂(A2)，其中，第一光聚合引发剂(A1)选自自由基型肟酯系光聚合引发剂、自由基型咪唑系光聚合引发剂、烷基苯酮系光聚合引发剂和酰基氧化膦系光聚合引发剂组成的组中的一种或几种，第二光聚合引发剂(A2)具有如通式(I)所示的结构：
Figure PCTCN2021124164-appb-000002
式(I)中，两个R 1各自独立地选自氢、C 1～C 10的直链或支链烷基、C 2～C 10的链烯基，或两个R 1形成环状结构；R 2和R 3相互独立地表示C 1～C 10的直链或支链烷基；R 4表示光活性基团；A表示氢、硝基、卤素或-CO-CR 2R 3R 4基团。
采用第一光聚合引发剂(A1)和第二光聚合引发剂(A2)具有更好的光引发活性和稳定性，将其作为光聚合引发剂(A)能够和含羧基树脂(B)及光聚合性单体(C)进行更深程度的固化，进而有利于提高其形成的固化物的耐热性和密着性。含羧基树脂(B)能使固化性树脂组合物成为可碱显影的固化性树脂组合物，并提高其显影图案的分辨率。光聚合性单体(C)的加入可以调整上述固化性组合物的耐化性能和固化速率。在此基础上，上述组合物无论在厚涂层还是在着色剂含量较高的体系中均具有优异的固化性，同时还具有高的分辨率和较好的耐热性、耐化性以及密着性。
光聚合引发剂(A)
作为前述组合特定的光聚合引发剂(A)，其中，光聚合引发剂(A)包括第一光聚合引发剂(A1)和第二光聚合引发剂(A2)，第一光聚合引发剂(A1)含有：自由基型咪唑系光聚合引发剂、自由基型肟酯系光聚合引发剂、烷基苯酮系光聚合引发剂、酰基氧化膦系光聚合引发剂组组成的组中的一种或几种，第二光聚合引发剂(A2)具有如通式(I)所示的结构：
Figure PCTCN2021124164-appb-000003
式(I)中，两个R 1分别独立地表示氢、C 1-C 10的直链或支链烷基或C 2-C 10的链烯基，或两个R 1也可以相连成环；R 2和R 3相互独立地表示C 1-C 10的直链或支链烷基；R 4表示光活性基团；A表示氢、硝基、卤素或-CO-CR 2R 3R 4基团。
在一种优选的实施例中，式(I)中，两个R 1各自独立地选自氢、C 1～C 6的直链或支链烷基或C 2～C 6的链烯基，或两个R 1形成四元环、五元环或六元环。
在一种优选的实施例中，式(I)中，R 2和R 3相互独立地表示C 1-C 6的直链或支链烷基。
在一种优选的实施例中，式(I)中，R 4为羟基或N-吗啉基。
在一种优选的实施例中，A为氢或-CO-CR 2R 3R 4基团，且取代基-CO-CR 2R 3R 4基团中R 2、R 3和R 4与前述相应部分具有相同的定义。
在一种优选的实施例中，自由基型咪唑系光聚合引发剂为双咪唑类光引发剂；更优选地，上述双咪唑类光引发剂包括但不限于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-二咪唑和2,2’-二(2,4-二氯苯基)-4,4’,5,5’-四苯基-二咪唑组成的组中的一种或多种。
在一种优选的实施例中，自由基型肟酯系光聚合引发剂包括但不限于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-乙酸肟和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-乙氧甲酰肟酯组成的组中的一种或多种。或者上述自由基型肟酯系光聚合引发剂也可以选自市售品的BASFJAPANLTD.制造的CGI-325、IRGACUREOXE01、IRGACUREOXE02、ADEKACORPORATION制造的N-1919等。
在一种优选的实施例中，烷基苯酮系光聚合引发剂包括但不限于苯偶酰二甲基缩酮系光聚合引发剂、α-羟基烷基苯酮系光聚合引发剂、α-氨基苯乙酮系光聚合引发剂和酰基氧化膦系光聚合引发剂组成的组中的一种或多种。
更优选地，苯偶酰二甲基缩酮系光聚合引发剂包括但不限于2,2-二甲氧基-1,2-二苯基乙烷-1-酮；作为苯偶酰二甲基缩酮系光聚合引发剂的市售品，可以举出：BASFJAPANLTD.制造的IRGACURE651等。
更优选地，α-羟基烷基苯酮系光聚合引发剂包括但不限于1-羟基-环己基-苯基-酮、2-羟基-2-甲基-1-苯基-丙烷-1-酮、1-[4-(2-羟基乙氧基)-苯基]-2-羟基-2-甲基-1-丙烷-1-酮和2-羟基-1-{4-[4-(2-羟基-2-甲基-丙酰基)-苄基]苯基}-2-甲基-丙烷-1-酮组成的组中的一种或多种；作为α-羟基烷基苯酮系光聚合引发剂的市售品，可以举出：BASFJAPANLTD.制造的IRGACURE184、DAROCUR1173、IRGACURE2959、IRGACURE127等。
更优选地，α-氨基苯乙酮系光聚合引发剂包括但不限于2-甲基-1-[4-(甲硫基)苯基]-2-吗啉代丙酮-1、2-苄基-2-二甲基氨基-1-(4-吗啉代苯基)-丁烷-1-酮、2-(二甲基氨基)-2-[(4-甲基苯基)甲基]-1-[4-(4-吗啉基)苯基]-1-丁酮、N,N-二甲基氨基苯乙酮。作为α-氨基苯乙酮系光聚合引发 剂的市售品，可以举出：BASFJAPANLTD.制造的IRGACURE907、IRGACURE369、IRGACURE379等。
更优选地，酰基氧化膦系光聚合引发剂包括但不限于2,4,6-三甲基苯甲酰基二苯基氧化膦、双(2,4,6-三甲基苯甲酰基)-苯基氧化膦和/或双(2,6-二甲氧基苯甲酰基)-2,4,4-三甲基-戊基氧化膦等。作为酰基氧化膦系光聚合引发剂的市售品，可以举出：BASFJAPANLTD.制造的TPO、819等。
优选地，第一光聚合引发剂(A1)为咪唑系光引发剂。
使用前述各光聚合引发剂时的配混量以固体成分换算，在一种优选的实施例中，在固化性树脂组合物中的光聚合引发剂的重量百分含量为2～25wt％，更优选为2.5～10wt％。
在一种优选的实施例中，第一光聚合引发剂(A1)和第二光聚合引发剂(A2)的重量比为(0.5～5)：(5～9.5)。
含羧基树脂(B)
含羧基树脂能使固化性树脂组合物成为可碱显影的固化性树脂组合物，并在显影时获得较高的分辨率。作为含羧基树脂(B)并没有特别的限制，可采用阻焊剂用、层间绝缘层用的固化性树脂组合物中所使用的公知的含羧基树脂。
为了进一步提高固化性组合物的光固化性和耐显影性，优选地，上述含羧基树脂中除羧基之外，还具有烯属不饱和键。更优选地，上述烯属不饱和双键为源自丙烯酸或者甲基丙烯酸或它们的衍生物的双键。或者当含羧基树脂(B)不具有烯属不饱和键时，为了提高固化性组合物的光固化性，可以在上述组合物中加入分子中具有1个以上烯属不饱和基团的化合物(光反应性单体)。
在一种优选的实施例中，作为上述分子中含有羧基、且分子内不具有烯属不饱和键的含羧基树脂包括但不限于以下几种：
(1)使丙烯酸、甲基丙烯酸等不饱和羧酸与苯乙烯、α-甲基苯乙烯、(甲基)丙烯酸低级烷基酯、异丁烯等具有不饱和双键的化合物共聚而得到的含羧基树脂；
(2)使具有不饱和双键的化合物与(甲基)丙烯酸缩水甘油酯的共聚物的环氧基、与1分子中具有1个羧基且不具有烯属不饱和键的有机酸，例如碳原子数为2～17的烷基羧酸、含芳香族基的烷基羧酸等反应，所生成的仲羟基与饱和或不饱和多元酸酐反应而得到的含羧基树脂；
(3)使含羟基聚合物、例如烯烃系含羟基聚合物、丙烯酸类多元醇、橡胶系多元醇、聚乙烯醇缩醛、苯乙烯烯丙醇系树脂、纤维素类等与饱和或不饱和多元酸酐反应而得到的含羧基树脂；
(4)使双酚A型环氧树脂、双酚F型环氧树脂、双酚S型环氧树脂、溴化双酚A型环氧树脂、氢化双酚A型环氧树脂、联苯酚型环氧树脂、联二甲苯酚型环氧树脂等双环氧化合物与 乙二酸、丙二酸、丁二酸、邻苯二甲酸、间苯二甲酸等二羧酸的反应产物、与饱和或不饱和多元酸酐反应而得到的含羧基树脂；
(5)使二官能环氧化合物与双酚A、双酚F等双酚类的反应产物、与饱和或不饱和多元酸酐反应而得到的含羧基树脂等。
在一种优选的实施例中，作为前述分子中具有羧基和分子内具有烯属不饱和键的含羧基树脂包括但不限于以下几种：
(1)使酚醛清漆型环氧树脂等1分子中至少具有两个环氧基的多官能环氧化合物与(甲基)丙烯酸等不饱和单羧酸反应，所生成的羟基再与六氢邻苯二甲酸酐、四氢邻苯二甲酸酐等饱和或不饱和多元酸酐反应而得到的含羧基树脂；
(2)使酚醛清漆型环氧树脂等1分子中至少具有两个环氧基的多官能环氧化合物、与(甲基)丙烯酸等不饱和单羧酸和壬基酚等1分子中具有与环氧基反应的醇羟基以外的1个反应性基团的化合物、更优选对羟基苯乙醇等1分子中具有至少1个醇羟基和与环氧基反应的醇羟基以外的1个反应性基团的化合物反应后，与六氢邻苯二甲酸酐、四氢邻苯二甲酸酐等饱和或不饱和多元酸酐反应而得到的含羧基树脂；
(3)使(甲基)丙烯酸、马来酸等不饱和羧酸与(甲基)丙烯酸甲酯等光聚合性单体的共聚物的羧基的一部分、与(甲基)丙烯酸缩水甘油酯等1分子中具有1个环氧基和烯属不饱和双键的化合物反应而得到的含羧基的树脂；
(4)使(甲基)丙烯酸、马来酸等不饱和羧酸与(甲基)丙烯酸甲酯等光聚合性单体的共聚物、与(甲基)丙烯酸缩水甘油酯等1分子中具有1个环氧基和烯属不饱和双键的化合物反应，所生成的羟基与六氢邻苯二甲酸酐、四氢邻苯二甲酸酐等饱和或不饱和多元酸酐反应而得到的含羧基树脂；
(5)使马来酸酐等不饱和二元酸酐与(甲基)丙烯酸甲酯等光聚合性单体的共聚物、与(甲基)丙烯酸-2-羟乙酯等(甲基)丙烯酸羟烷基酯反应而得到的含羧基树脂等。
此外，上述树脂的合成中使用的多官能团环氧化合物为具有双酚A结构、双酚F结构、联苯酚结构、联苯酚酚醛清漆结构、联二甲苯酚结构、特别是具有联苯基酚醛清漆结构的化合物以及其氢化物时，得到的固化性树脂组合物的固化物因低翘曲、耐弯曲性优异而优选。
要说明的是，此处的(甲基)丙烯酸酯是总称丙烯酸酯、甲基丙烯酸酯以及它们的混合物的术语，对于以下其他类似的表达也是同样的。
此外，上述含羧基树脂的酸值优选为20～200mgKOH/g的范围，更优选为40～150mgKOH/g的范围。含羧基树脂的酸值为20mgKOH/g以上时，能够获得涂膜的密合性，在形成固化性树脂组合物的情况下碱显影性良好。此外，酸值为200mgKOH/g以下时，可抑制显影液引起的曝光部的溶解，不会使线变得比所需要的细，此外，可抑制曝光部与未曝光部无区别地被显影液溶解剥离，因此正常的抗蚀图案的描绘变得容易。
上述含羧基树脂的重均分子量根据树脂骨架而不同，优选地，含羧基树脂的重均分子量为2000～150000。若重均分子量为2000以上，则不粘性能优异，曝光后的涂膜的耐湿性良好，显影时不会产生膜减少，分辨率良好。此外，若重均分子量为150000以下，则成为显影性良好、贮藏稳定性也优异的物质。更优选地，含羧基树脂的重均分子量为5000～100000。
光聚合性单体(C)
光聚合性单体是经活性能量射线照射而进行光固化后，使上述含羧基树脂不溶化、或有助于不溶化于碱性水溶液中的化合物，光聚合性单体(C)也可以作为固化性树脂组合物的稀释剂使用。
作为上述光聚合性单体可以使本领域常用的种类。比如(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸环己酯等(甲基)丙烯酸烷基酯类有机物；(甲基)丙烯酸2-羟基乙酯、(甲基)丙烯酸2-羟基丙酯等(甲基)丙烯酸羟烷基酯类有机物；乙二醇、丙二醇、二甘醇、二丙二醇等烯化氧衍生物的单或二(甲基)丙烯酸酯类有机物；己二醇、三羟甲基丙烷、季戊四醇、二(三羟甲基丙烷)、二(季戊四醇)、三羟乙基异氰脲酸酯等多元醇或它们的环氧乙烷或环氧丙烷加成物的多元(甲基)丙烯酸酯类有机物；(甲基)丙烯酸苯氧基乙酯、双酚A的聚氧二(甲基)丙烯酸酯等酚类的环氧乙烷或环氧丙烷加成物的(甲基)丙烯酸酯；甘油二缩水甘油醚、三羟甲基丙烷三缩水甘油醚、异氰脲酸三缩水甘油酯等缩水甘油醚的(甲基)丙烯酸酯；和蜜胺(甲基)丙烯酸酯等。
上述光聚合性单体(C)可以单独使用一种、也可以组合两种以上使用。上述光聚合性单体(C)的配混量以固体成分换算，优选地，在固化性树脂组合物光聚合性单体(C)的重量百分含量为1～30wt％。若为30重量％以下，则表面不会发粘，指触干燥性良好。此外，若为1重量％以上，则曝光时能得到充分的光固化性，且图案形成性良好。为了进一步提高固化性组合物形成的固化物在实干时间和光固化充分程度，更优选地，光聚合性单体(C)的重量百分含量为2～20wt％，进一步优选为5～15wt％。
热固化性成分(D)
为了提高固化性树脂组合物形成的固化物的耐热性，优选地，上述固化性树脂组合物还包括热固化性成分(D)。在一种优选的实施例中，热固化性成分(D)包括但不限于封端异氰酸酯化合物、氨基树脂、马来酰亚胺化合物、苯并噁嗪树脂、碳二亚胺树脂、环碳酸酯化合物、多官能环氧化合物、多官能氧杂环丁烷化合物和环硫树脂组成的组中的一种或多种。
在一种优选的实施例中，上述多官能环氧化合物包括但不限于环氧化植物油、双酚A型环氧树脂、氢醌型环氧树脂、双酚型环氧树脂、硫醚型环氧树脂、溴化环氧树脂、酚醛清漆型环氧树脂、联苯酚酚醛清漆型环氧树脂、双酚F型环氧树脂、氢化双酚A型环氧树脂、缩水甘油胺型环氧树脂、乙内酰脲型环氧树脂、脂环式环氧树脂、三羟基苯基甲烷型环氧树脂、双酚S型环氧树脂、双酚A酚醛清漆型环氧树脂、四苯酚乙烷型环氧树脂、杂环式环氧树脂、邻苯二甲酸二缩水甘油酯树脂、四缩水甘油基二甲苯酚乙烷树脂、含萘基环氧树脂、具有双环戊二烯骨架的环氧树脂、甲基丙烯酸缩水甘油酯共聚系环氧树脂、环己基马来酰亚胺与甲基丙烯酸缩水甘油酯的共聚环氧树脂、环氧改性的聚丁二烯橡胶衍生物、端羧基液体丁腈橡 胶改性环氧树脂(CTBN改性环氧树脂)、联二甲苯酚型和/或联苯酚型环氧树脂。这些环氧树脂可以单独使用或可以组合两种以上使用。在它们中，特别优选双酚型环氧树脂。
在一种优选的实施例中，多官能氧杂环丁烷化合物包括但不限于多官能氧杂环丁烷类化合物、具有羟基的树脂的醚化物和具有氧杂环丁烷环的不饱和单体与(甲基)丙烯酸烷基酯的共聚物组成的组中的一种或多种。
更优选地，多官能氧杂环丁烷类包括但不限于双[(3-甲基-3-氧杂环丁烷基甲氧基)甲基]醚、双[(3-乙基-3-氧杂环丁烷基甲氧基)甲基]醚、1,4-双[(3-甲基-3-氧杂环丁烷基甲氧基)甲基]苯、1,4-双[(3-乙基-3-氧杂环丁烷基甲氧基)甲基]苯、丙烯酸(3-甲基-3-氧杂环丁烷基)甲酯、丙烯酸(3-乙基-3-氧杂环丁烷基)甲酯、甲基丙烯酸(3-甲基-3-氧杂环丁烷基)甲酯、甲基丙烯酸(3-乙基-3-氧杂环丁烷基)甲酯、或它们的低聚物或共聚物组成的组中的一种或多种。
更优选地，具有羟基的树脂的醚化物包括但不限于氧杂环丁醇、酚醛清漆树脂、聚(对羟基苯乙烯)、cardo型双酚类化合物、杯芳烃类化合物、间苯二酚杯芳烃类化合物、或倍半硅氧烷。
具有多个环状硫醚基的环硫树脂包括但不限于三菱化学株式会社制造的YL7000(双酚A型环硫树脂)、东都化成株式会社制造的YSLV-120TE等。此外，也可以采用同样的合成方法将酚醛清漆型环氧树脂的环氧基的氧原子替换为硫原子的环硫树脂等。作为市售的环氧树脂，可以举出例如三菱化学株式会社制造的jER828、806、807、YX-8000、8034、jER834、新日铁住金株式会社制造的YD-128、YDF-170、ZX-1059、ST-3000、DIC株式会社制造的830、835、840、850、N-730A、N695和日本化药株式会社制造的RE-306等。
为了提高固化性组合物的固化速率，缩短实干时间，在一种优选的实施例中，除了上述热固化性树脂成分之外，本发明的固化性树脂组合物还包括热固化性催化剂。只要能够实现上述目的的化合物均可用作热固化催化剂。更优选地，上述热固化性催化剂包括但不限于咪唑衍生物、胺类化合物、肼类化合物、有机膦、三聚氰胺、胍胺类化合物和均三嗪类化合物组成的组中的一种或多种。其中咪唑衍生物包括但不限于咪唑、2-甲基咪唑、2-乙基咪唑、2-乙基-4-甲基咪唑、2-苯基咪唑、4-苯基咪唑、1-氰乙基-2-苯基咪唑和1-(2-氰乙基)-2-乙基-4-甲基咪唑组成的组中的一种或多种；胺化合物包括但不限于双氰胺、苄基二甲胺、4-(二甲基氨基)-N,N-二甲基苄基胺、4-甲氧基-N,N-二甲基苄基胺和4-甲基-N,N-二甲基苄基胺组成的组中的一种或多种；肼化合物包括但不限于己二酸二酰肼和/或癸二酸二酰肼；有机磷包括但不限于三苯基膦。胍胺类化合物包括但不限于胍胺和/或苯胍胺)。均三嗪衍生物包括但不限于2,4-二氨基-6-甲基-1,3,5-三嗪、2,4-二氨基-6-甲基丙烯酰氧基乙基-均三嗪、2-乙烯基-2,4-二氨基-均三嗪、2-乙烯基-4,6-二氨基-均三嗪·异氰脲酸加成物、2,4-二氨基-6-甲基丙烯酰氧基乙基-均三嗪·异氰脲酸加成物组成的组中的一种或多种。
其他的成分
为了进一步提高固化性树脂组合物的综合性能，优选地，固化性树脂组合物还包括添加剂，更优选地，添加剂选自热聚合抑制剂、紫外线吸收剂、硅烷偶联剂、增塑剂、阻燃剂、 抗静电剂、防老化剂、抗菌/防霉剂、消泡剂、流平剂、填料、增稠剂、密合性赋予剂、触变性赋予剂、着色剂、增感剂、供氢体及溶剂组成的组中的一种或多种。
填料
本发明的固化性树脂组合物也可以含有填料(无机填充剂)。填料是为了抑制固化性树脂组合物的固化物的固化收缩，且使密合性、硬度等特性提高而使用的。作为填料，例如可以举出：硫酸钡、无定形硅石、熔融硅石、球状硅石、滑石、粘土、碳酸镁、碳酸钙、氧化铝、氢氧化铝、氮化硅、氮化铝、氮化硼、诺易堡硅土等。
填料的平均粒径(D50)优选为1μm以下、更优选为0.7μm以下、进一步优选为0.5μm以下。平均粒径超过1μm时，有固化性树脂组合物呈白浊的担心，可以依据实际用途进行选择。平均粒径(D50)可以利用激光衍射/散射法进行测定。通过平均粒径处于上述范围，折射率将会趋近于树脂成分，透射性提高。
溶剂
作为有机溶剂，可以使用公知的物质。另外，有机溶剂可以单独使用1种，也可以2种及以上混合使用。优选地，有机溶剂包括但不限于以下一种或多种：甲乙酮、环己酮等酮类溶剂；甲苯、二甲苯、四甲苯等芳香族烃类溶剂；溶纤剂、甲基溶纤剂、丁基溶纤剂、卡必醇、甲基卡必醇、丁基卡必醇、丙二醇单甲醚、二丙二醇单甲醚、二丙二醇二乙醚、二乙二醇单甲醚乙酸酯、三丙二醇单甲醚等二醇醚类溶剂；乙酸乙酯、乙酸丁酯、乳酸丁酯、溶纤剂乙酸酯、丁基溶纤剂乙酸酯、卡必醇乙酸酯、丁基卡必醇乙酸酯、丙二醇单甲醚乙酸酯、二丙二醇单甲醚乙酸酯、碳酸亚丙酯等酯类溶剂；辛烷和癸烷等脂肪族烃类溶剂；石油醚、石脑油、溶剂石脑油等石油系溶剂等。
有机溶剂一般出于制备组合物、形成干膜、涂布于印刷电路基板上时的粘度调整等目的而使用。因此，有机溶剂的含量可以根据目的而适宜变更。
增感剂
作为增感剂可包括(但不限于)：蒽类光引发剂、香豆素类光引发剂、噻吨酮类光引发剂、吖啶类光引发剂及其它本领域技术人员已知的光引发剂。
在一种优选的实施例中，蒽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。
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。
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。
上述增感剂可以单独使用或配混使用，在固化性树脂组合物中，增感剂的重量百分含量为0.01-10wt％，优选为0.01-5wt％。增感剂的含量包括但不限于上述范围，而将其限定在上述范围内，有利于进一步提高固化性树脂组合物的感光度。
供氢体
如前文所述本发明的固化性树脂组合物的特征在于组合特定的光引发剂可以提高组合物的固化性能，尤其优选咪唑类化合物与通式(I)化合物配合使用。此时为了改善感光度，优选地，上述固化性组合物还包括供氢体。双咪唑类化合物经光照后裂解，产生的单咪唑自由基体积较大，位阻效应使得活性较小，很难单独引发单体聚合，而如果和供氢体配合使用，则单咪唑自由基容易夺取供氢体上的活泼氢，产生新的活性自由基，进而引发单体聚合。
只要是具有上述特性的供氢体，在具体种类方面就没有特别限制，可以包括(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等。这些化合物可单独使用，或以其中的两种以上组合使用。
胺类化合物没有特别限制，可以包括(但不限于)：脂肪族胺化合物，如三乙醇胺、甲基二乙醇胺、三异丙醇胺等；芳香族胺化合物，如4-二甲氨基苯甲酸甲酯、4-二甲氨基苯甲酸乙酯、4-二甲氨基苯甲酸异戊酯、4-二甲氨基苯甲酸2-乙基己酯、2-二甲氨基乙基苯甲酸酯、N,N-二甲基对甲苯胺、4,4’-双(二甲氨基)二苯甲酮、4,4’-双(二乙氨基)二苯甲酮等。
羧酸类化合物没有特别限制，可以包括(但不限于)：芳香族杂乙酸、苯基硫代乙酸、甲基苯基硫代乙酸、乙基苯基硫代乙酸、甲基乙基苯基硫代乙酸、二甲基苯基硫代乙酸、甲氧基苯基硫代乙酸、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、萘氧基乙酸等。
含有巯基的有机硫化合物没有特别限制，可以包括(但不限于)：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)、1,2-丙二醇双(3-巯基丁酸酯)、二乙二醇双(3-巯基丁酸酯)、丁二醇双(3-巯基丁酸酯)、辛二醇双(3-巯基丁酸酯)、三羟甲基丙烷三(3-巯基丁酸酯)、季戊四醇四(3-巯基丁酸酯)、二季戊四醇六(3-巯基丁酸酯)、乙二醇双(2-巯基丙酸酯)、丙二醇双(2-巯基丙酸酯)、二乙二醇双(2-巯基丙酸酯)、丁二醇双(2-巯基丙酸酯)、 辛二醇双(2-巯基丙酸酯)、三羟甲基丙烷三(2-巯基丙酸酯)、季戊四醇四(3-巯基丙酸酯)、二季戊四醇六(2-巯基丙酸酯)、乙二醇双(3-巯基异丁酸酯)、1,2-丙二醇双(3-巯基异丁酸酯)、二乙二醇双(3-巯基异丁酸酯)、丁二醇双(3-巯基异丁酸酯)、辛二醇双(3-巯基异丁酸酯)、三羟甲基丙烷三(3-巯基异丁酸酯)、季戊四醇四(3-巯基异丁酸酯)、二季戊四醇六(3-巯基异丁酸酯)、乙二醇双(2-巯基异丁酸酯)、1,2-丙二醇双(2-巯基异丁酸酯)、二乙二醇双(2-巯基异丁酸酯)、丁二醇双(2-巯基异丁酸酯)、辛二醇双(2-巯基异丁酸酯)、三羟甲基丙烷三(2-巯基异丁酸酯)、季戊四醇四(2-巯基异丁酸酯)、二季戊四醇六(2-巯基异丁酸酯)、乙二醇双(4-巯基戊酸酯)、1,2-丙二醇双(4-巯基异戊酸酯)、二乙二醇双(4-巯基戊酸酯)、丁二醇双(4-巯基戊酸酯)、辛二醇双(4-巯基戊酸酯)、三羟甲基丙烷三(4-巯基戊酸酯)、季戊四醇四(4-巯基戊酸酯)、二季戊四醇六(4-巯基戊酸酯)、乙二醇双(3-巯基戊酸酯)、1,2-丙二醇双(3-巯基戊酸酯)、二乙二醇双(3-巯基戊酸酯)、丁二醇双(3-巯基戊酸酯)、辛二醇双(3-巯基戊酸酯)、三羟甲基丙烷三(3-巯基戊酸酯)、季戊四醇四(3-巯基戊酸酯)、二季戊四醇六(3-巯基戊酸酯)等脂肪族二级多官能硫醇化合物；芳香族二级多官能硫醇化合物，如邻苯二甲酸二(1-巯基乙酯)、邻苯二甲酸二(2-巯基丙酯)、邻苯二甲酸二(3-巯基丁酯)、邻苯二甲酸二(3-巯基异丁酯)等。
醇类化合物没有特别限制，可以包括(但不限于)：甲醇、乙醇、1-丙醇、2-丙醇、1-丁醇、2-丁醇、新戊醇、正己醇、环已醇、乙二醇、1,2-丙二醇、1,2,3-丙三醇、苯甲醇、苯乙醇等。
在固化性树脂组合物中，供氢体的重量百分含量为0.01-20wt％，优选为0.01-10wt％。当供氢体的含量在上述范围内，对调控固化性树脂组合物的感光度是有利的。
着色剂
本发明的固化性树脂组合物可以配混着色剂。作为着色剂，可以使用红、蓝、绿、黄等公知的着色剂，可以是颜料、染料、色素中的任意一种。具体地，可列举出带有下述的染料索引(C.I.；TheSocietyofDyersandColourists发行)序号的物质。其中，从降低环境负荷以及对人体的影响的观点出发，优选不含有卤素。
红色着色剂:
作为红色着色剂，有单偶氮系、双偶氮系、偶氮色淀系、苯并咪唑酮系、苝系、二酮基吡咯并吡咯系、缩合偶氮系、蒽醌系、喹吖啶酮系等，具体地，可列举出以下物质。
单偶氮系：颜料红1、2、3、4、5、6、8、9、12、14、15、16、17、21、22、23、31、32、112、114、146、147、151、170、184、187、188、193、210、245、253、258、266、267、268、269。
双偶氮系：颜料红37、38、41。
单偶氮色淀系：颜料红48:1、48:2、48:3、48:4、49:1、49:2、50:1、52:1、52:2、53:1、53:2、57:1、58:4、63:1、63:2、64:1、68。
苯并咪唑酮系：颜料红171、颜料红175、颜料红176、颜料红185、颜料红208。
苝系：溶剂红135、溶剂红179、颜料红123、颜料红149、颜料红166、颜料红178、颜料红179、颜料红190、颜料红194、颜料红224。
二酮基吡咯并吡咯系：颜料红254、颜料红255、颜料红264、颜料红270、颜料红272。
缩合偶氮系：颜料红220、颜料红144、颜料红166、颜料红214、颜料红220、颜料红221、颜料红242。
蒽醌系：颜料红168、颜料红177、颜料红216、溶剂红149、溶剂红150、溶剂红52、溶剂红207。
喹吖啶酮系：颜料红122、颜料红202、颜料红206、颜料红207、颜料红209。
蓝色着色剂:
作为蓝色着色剂，有酞菁系、蒽醌系，颜料系是被分类为颜料(Pigment)的化合物，具体可列举出如下物质：颜料蓝15、颜料蓝15:1、颜料蓝15:2、颜料蓝15:3、颜料蓝15:4、颜料蓝15:6、颜料蓝16、颜料蓝60。
作为染料系，可使用溶剂蓝35、溶剂蓝63、溶剂蓝68、溶剂蓝70、溶剂蓝83、溶剂蓝87、溶剂蓝94、溶剂蓝97、溶剂蓝122、溶剂蓝136、溶剂蓝67、溶剂蓝70等。除了上述以外，还可以使用金属取代或者未取代的酞菁化合物。
绿色着色剂:
作为绿色着色剂，同样有酞菁系、蒽醌系、苝系，具体地，可使用颜料绿7、颜料绿36、溶剂绿3、溶剂绿5、溶剂绿20、溶剂绿28等。除了上述以外，还可以使用金属取代或者未取代的酞菁化合物。
黄色着色剂:
作为黄色着色剂，有单偶氮系、双偶氮系、缩合偶氮系、苯并咪唑酮系、异吲哚啉酮系、蒽醌系等，具体地，可列举出以下物质。
蒽醌系：溶剂黄163、颜料黄24、颜料黄108、颜料黄193、颜料黄147、颜料黄199、颜料黄202。
异吲哚啉酮系：颜料黄110、颜料黄109、颜料黄139、颜料黄179、颜料黄185。
缩合偶氮系：颜料黄93、颜料黄94、颜料黄95、颜料黄128、颜料黄155、颜料黄166、颜料黄180。
苯并咪唑酮系：颜料黄120、颜料黄151、颜料黄154、颜料黄156、颜料黄175、颜料黄181。
单偶氮系：颜料黄1、2、3、4、5、6、9、10、12、61、62、62:1、65、73、74、75、97、100、104、105、111、116、167、168、169、182、183。
双偶氮系：颜料黄12、13、14、16、17、55、63、81、83、87、126、127、152、170、172、174、176、188、198。
另外，为了调整色调，可以加入紫、橙、棕色、黑等的着色剂。
具体例示的话，有颜料紫19、23、29、32、36、38、42，溶剂紫13、36、C.I.颜料橙1、C.I.颜料橙5、C.I.颜料橙13、C.I.颜料橙14、C.I.颜料橙16、C.I.颜料橙17、C.I.颜料橙24、C.I.颜料橙34、C.I.颜料橙36、C.I.颜料橙38、C.I.颜料橙40、C.I.颜料橙43、C.I.颜料橙46、C.I.颜料橙49、C.I.颜料橙51、C.I.颜料橙61、C.I.颜料橙63、C.I.颜料橙64、C.I.颜料橙71、C.I.颜料橙73、C.I.颜料棕23、C.I.颜料棕25、C.I.颜料黑1、C.I.颜料黑7等。
在一种优选的实施例中，着色剂可以适当配混，固化性组合物中，含羧基树脂(B)或热固化性成分(D)与着色剂的重量比大于100：10，更优选为100：(0.1～5)。
本发明的固化性树脂组合物可以进行干膜化而使用，也可以以液态形式直接使用。以液态的形式使用时，可以为单组分性也可以为双组分性以上。
本发明的固化性树脂组合物可用于形成作为阻焊层、覆盖层、层间绝缘层等的印刷电路板的永久覆膜的图案层，特别是对形成阻焊层有用。另外，即使为薄膜也可以形成涂膜强度优异的固化物，因此，本发明的固化性树脂组合物也可以适合用于要求薄膜化的印刷电路板、例如IC封装基板(IC封装中使用的印刷电路板)中的图案层的形成。进而，由本发明的固化性树脂组合物得到的固化物具有高弹性模量和低CTE(膨胀系数)的优点，因而也可以适用于形成总厚度薄而刚性不足的IC封装基板中的图案层。
本发明的固化性树脂组合物也可以制成干膜的形态，该干膜具备：载体膜(支撑体)、和形成于该载体膜上的由上述固化性树脂组合物形成的树脂层。进行干膜化时，将本发明的固化性树脂组合物用上述有机溶剂稀释以调节至适当的粘度，通过逗点涂布机(comma coater)、刮刀涂布机、唇口涂布机(lip coater)、棒涂机(rod coater)、挤压涂布机(squeeze coater)、逆式涂布机(reverse coater)、传递辊涂布机(transfer rollcater)、凹版涂布机(gravure coater)或喷涂机在载体膜上涂布成均匀的厚度，通常在50～130℃的温度下干燥1～30min而获得膜。对于涂布膜厚没有特别的限制，通常，以干燥后的膜厚计，在1～150μm、优选10～60μm的范围内适当选择。
作为载体膜，可以使用塑料薄膜，优选使用聚对苯二甲酸乙二醇酯等聚酯薄膜、聚酰亚胺薄膜、聚酰胺酰亚胺薄膜、聚丙烯薄膜、聚苯乙烯薄膜等塑料薄膜。对于载体膜的厚度没有特别的限制，通常在10～150μm的范围内适当选择。
在载体膜上形成本发明的固化性树脂组合物的树脂层后，为了防止树脂层的表面附着灰尘等，进一步优选在树脂层的表面层叠可剥离的覆盖膜。作为可剥离的覆盖膜，例如可以使 用聚乙烯薄膜、聚四氟乙烯薄膜、聚丙烯薄膜、经表面处理的纸等，只要在剥离覆盖膜时树脂层与覆盖膜的粘接力小于树脂层与载体膜的粘接力即可。
本发明的印刷电路板具有由本发明的固化性树脂组合物或干膜的树脂层得到的固化物。作为本发明的印刷电路板的制造方法，例如，使用上述有机溶剂将本发明的固化性树脂组合物调节到适于涂布方法的粘度，利用浸涂法、流涂法、辊涂法、棒涂法、丝网印刷法或帘涂法等方法涂布到基材上，然后在60～100℃的温度下使组合物中所含的有机溶剂挥发干燥(暂时干燥)，从而形成不粘的树脂层。另外，在为干膜的情况下，利用层压机等以树脂层与基材接触的方式贴合于基材上，然后剥离载体膜，由此在基材上形成树脂层。
作为上述基材，除了预先通过铜等形成有电路的印刷电路板、柔性印刷电路板以外，还可列举出使用了纸-酚醛树脂、纸-环氧树脂、玻璃布-环氧树脂、玻璃-聚酰亚胺、玻璃布/无纺布-环氧树脂、玻璃布/纸-环氧树脂、合成纤维-环氧树脂、氟树脂·聚乙烯·聚苯醚(聚亚苯基氧化物)·氰酸酯等的高频电路用覆铜层叠板等材质的所有等级(FR-4等)的覆铜层叠板、以及金属基板、聚酰亚胺薄膜、PET薄膜、聚萘二甲酸乙二醇酯(PEN)薄膜、玻璃基板、陶瓷基板、晶圆板等。
涂布本发明的固化性树脂组合物后进行的挥发干燥可以使用热风循环式干燥炉、IR炉、热板、对流烘箱等(使用具有利用蒸气的空气加热方式的热源的装置，使干燥机内的热风对流接触的方法和通过喷嘴吹送至支撑体的方式)来进行。
基材上形成树脂层后，通过形成有规定图案的光掩模、利用活性能量射线选择性地进行曝光，通过稀碱水溶液(例如，0.3～3重量％碳酸钠水溶液)将未曝光部显影，从而形成固化物的图案。进而，对固化物照射活性能量射线后进行加热固化(例如，100～220℃)、或加热固化后照射活性能量射线、或仅进行加热固化而使其最终完成固化(完全固化)，由此形成密合性、硬度等各特性优异的固化膜。
作为用于上述活性能量射线照射的曝光机，只要为搭载有高压汞灯、LED光源、超高压汞灯、金属卤化物灯、水银短弧灯等并照射350～450nm范围的紫外线的装置即可，此外，还可以使用直接描绘装置(例如通过来自计算机的CAD数据、利用激光直接描绘图像的激光直接成像装置)。作为直描机的灯光源或激光源，只要最大波长处于350～410nm的范围内即可。用于形成图像的曝光量根据膜厚等而不同，通常可使其为10～1000mJ/cm 2、优选为20～800mJ/cm 2的范围内。
作为上述显影方法，可以使用浸渍法、淋洗法、喷雾法、刷涂法等，作为显影液，可以使用氢氧化钾、氢氧化钠、碳酸钠、碳酸钾、磷酸钠、硅酸钠、氨、胺类等的碱水溶液。
本发明的固化性树脂组合物不仅可以用于通过上述的显影液形成固化膜的图案的用途，还可以用于不形成图案的用途、例如模用途(密封用途)。
本申请的另一方面还提供了一种阻焊膜，阻焊膜采用本申请提供的固化性树脂组合物固化形成。上述组合物无论在厚涂层还是在着色剂含量较高的体系中均具有优异的固化性，同 时还具有高的分辨率和较好的耐热性、耐化性以及密着性。因而选用其制得的阻焊膜具有优异的耐热性、耐化性、密着性以及较高的分辨率。
本申请的又一方面还提供了一种印刷电路板，包括阻焊膜，该阻焊膜包括本申请提供的阻焊膜。由于本申请提供的阻焊膜具有优异的耐热性、耐化性、密着性以及较高的分辨率。因而在印刷电路板上设置上述阻焊膜，由于大大提升印刷电路板的外观美观性，减少着色剂的用量。
本申请的再一方面还提供了一种层间绝缘材料，层间绝缘材料采用本申请提供的固化性树脂组合物固化形成。上述组合物无论在厚涂层还是在着色剂含量较高的体系中均具有优异的固化性，同时还具有高的分辨率和较好的耐热性、耐化性以及密着性。因而选用其制得的层间绝缘材料具有优异的耐热性、耐化性、密着性以及较高的分辨率。
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。
具体实施方式
<固化性树脂组合物的制备>
以表1和2所示的组成(重量份)，将各成分用搅拌机进行预混合后，用三辊磨进行混磨，制备固化性树脂组合物。其中，对比例中的光聚合引发剂采用现行技术中常用的2-甲基-1-(4-甲硫基苯基)-2-吗啉-1-丙酮作为对比，以下，通过实施例和比较例，对本发明作进一步具体说明，但本发明不限定于下述实施例。
表1
Figure PCTCN2021124164-appb-000004
表2
Figure PCTCN2021124164-appb-000005
Figure PCTCN2021124164-appb-000006
表1和2中各组分代号表示的含义如表3中所示。
表3
Figure PCTCN2021124164-appb-000007
Figure PCTCN2021124164-appb-000008
固化性树脂组合物性能评价
1、<感光度评价>
将实施例及比较例的固化性树脂组合物通过丝网印刷法按照约25μm涂布到满铜基板上，在80℃的热风循环式干燥炉中干燥30min。将干燥后基板放置至达到室温后，分别使用搭载金属卤化物灯的曝光装置(ELS106SA)以150mj/cm 2和405nm LED曝光机(RW-UVAP202-20gl)以200mj/cm 2隔着阶段式曝光表(Stuffer21级)对该干燥涂膜进行曝光，读取进行60s显影(1wt％Na 2CO 3水溶液、30℃、0.2MPa)后残留的阶段式曝光表的图案。残留膜的段数越高，固化性组合物的感度越高。
2、<固化涂层外观>
用丝网印刷法将上述各实施例和比较例的组合物整面涂布到电路厚35μm的形成有图案的铜箔基板上，自然冷却至室温。以最佳曝光量150mj/cm 2对固化性树脂组合物进行曝光，然后进行150℃×60min的热固化，从而得到固化涂膜。肉眼观察固化涂层的外观；
○：涂层光滑平整，无皱缩
×：涂层表观不良，出现局部皱缩
3、<分辨率>
将前述实施例和比较例的固化性树脂组合物通过丝网印刷以干燥后的膜厚为25μm的方式整面地涂布到满铜基板上，在80℃下干燥30min。将干燥后基板放置至达到室温后，对该基板使用搭载有高压汞灯的曝光装置(ELS106SA)和以得到宽度为自30μm至100μm每隔10μm的阻焊图案的方式制作的专用负片进行150mJ/cm 2曝光，用30℃的1wt％碳酸钠水溶液在喷压0.2MPa的条件下进行60s显影，得到分辨率评价用抗蚀图案。
4、<耐焊接热性能、耐酸性、耐碱性评价用基板制作法>
将前述实施例及比较例的固化性树脂组合物利用丝网印刷整面地涂布在形成有图案的铜箔基板上，在80℃下干燥30min，自然冷却至室温。以最佳曝光量150mj/cm 2对固化性树脂组合物进行曝光，用30℃的1wt％碳酸钠水溶液在喷压0.2MPa的条件下进行60s显影，得到抗蚀图案。将该基板在130℃下加热60min使其固化，制成评价用基板。
＜耐焊接热性能＞
将固化漆膜涂布松香型助焊剂，使其浸没到288℃的铅锡炉中30s。用乙二醇丁醚擦洗表面，3M胶带(型号610#)撕拉三次，如无掉油则表示耐热OK，否则NG。
＜耐酸性＞
将评价基板在10vol％H 2SO 4水溶液中在室温下浸渍20min，通过目视确认浸渗、涂膜的溶出，进而确认由带剥离造成的剥脱。
○：未观察到变化
△：仅稍稍变化
×：涂膜存在鼓起或溶胀脱落
＜耐碱性＞
将评价基板在10vol％NaOH水溶液中在室温下浸渍20min，通过目视确认浸渗、涂膜的溶出，进而确认由带剥离造成的剥脱。
○：未观察到变化
△：稍微鼓起
×：涂膜存在溶胀脱落
＜耐溶剂性＞
将评价基板在丙二醇单甲醚中在室温下浸渍20min，通过目视确认浸渗、涂膜的溶出，进而确认由带剥离造成的剥脱。
○：未观察到变化
△：稍微鼓起
×：涂膜存在溶胀脱落
5、<密合性测试>
将实施例及比较例的固化性树脂组合物通过丝网印刷法按照约25μm涂布到经磨刷机打磨过的满铜基板上和聚酰亚胺上，在80℃的热风循环式干燥炉中干燥30min。将干燥后基板 放置至达到室温后，以最佳曝光量150mj/cm 2对固化性树脂组合物进行曝光，然后进行150℃×60min的热固化，从而得到固化涂膜。
根据国家标准《GBT9286-1998色漆和清漆漆膜的划痕实验》进行附着力测试，测试方法为：使用百格刀，刀口宽度约为10mm～12mm，每1mm～1.2mm为间隔，共有10格，直线划下时会出现10条间隔相同的直线刀痕，于直线刀痕的垂直位置划下，便成为10×10的100格的正方形，百格刀划下去时应深入到底材，不可只割在涂层上，否则测试不成立。当百格刀划完之后，使用3M公司生产的Transparent Tape 600胶带测试会不会脱落，首先，胶带贴于百格位置，以手指压下将胶带紧密贴附，再以瞬间的力道将胶带撕起，目视素材上的涂料是否有脱落现象。
评级方法和标准：
0级：切口的边缘完全光滑，格子边缘没有任何剥落。
1级：在切口的相交处有小片剥落，划格区内实际破损≤5％。
2级：切口的边缘和/或相交处有被剥落，其面积大于5％～15％。
3级：沿切口边缘有部分剥落或整大片剥落，或部分格子被整片剥落，剥落的面积超过15％～35％。
4级：切口边缘大片剥落/或者一些方格部分或全部剥落，其面积大于划格区的35％～65％。
5级：在划线的边缘及交叉点处有成片的油漆脱落，且脱落总面积大于65％。
评价结果如表4中所示。
表4
Figure PCTCN2021124164-appb-000009
由表4所示的结果可知，通过将双咪唑系第一光聚合引发剂、肟酯系第一光聚合引发剂、烷基苯酮系第一光聚合引发剂、酰基氧化膦系第一光聚合引发剂中的任意一种与上述通式(I) 所示的第二光聚合引发剂进行特定的组合，尤其是双咪唑系光引发剂与通式(I)组合而成的实施例的固化性树脂组合物在固化性方面性能优异，并且其他综合性能优异。
另外，实验研究发现，单独使用第一光聚合引发剂(A1)或第二光聚合引发剂(A2)应用在固化性树脂组合物中均存在感度低、不好显影的问题，因此本发明中不再提供单独使用第一光聚合引发剂(A1)或第二光聚合引发剂(A2)的对比例。
需要说明的是，本申请的说明书和权利要求书中的术语“第一”、“第二”等是用于区别类似的对象，而不必用于描述特定的顺序或先后次序。应该理解这样使用的术语在适当情况下可以互换，以便这里描述的本申请的实施方式例如能够以除了在这里描述的那些以外的顺序实施。
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 (10)

  1. 一种固化性树脂组合物，其特征在于，所述固化性树脂组合物包括光聚合引发剂(A)、含羧基树脂(B)和光聚合性单体(C)，光聚合引发剂(A)包括第一光聚合引发剂(A1)和第二光聚合引发剂(A2)，其中，所述第一光聚合引发剂(A1)选自自由基型肟酯系光聚合引发剂、自由基型咪唑系光聚合引发剂、烷基苯酮系光聚合引发剂和酰基氧化膦系光聚合引发剂组成的组中的一种或几种，所述第二光聚合引发剂(A2)具有如通式(I)所示的结构：
    Figure PCTCN2021124164-appb-100001
    式(I)中，两个R 1各自独立地选自氢、C 1～C 10的直链或支链烷基、或C 2～C 10的链烯基，或两个所述R 1形成环状结构；R 2和R 3相互独立地表示C 1～C 10的直链或支链烷基；R 4表示光活性基团；A表示氢、硝基、卤素或-CO-CR 2R 3R 4基团。
  2. 根据权利要求1所述的固化性树脂组合物，其特征在于，所述式(I)中，两个R 1各自独立地选自氢、C 1～C 6的直链或支链烷基或C 2～C 6的链烯基，或两个所述R 1形成四元环、五元环或六元环。
  3. 根据权利要求1或2所述的固化性树脂组合物，其特征在于，所述式(I)中，R 2和R 3相互独立地表示C 1-C 6的直链或支链烷基。
  4. 根据权利要求3所述的固化性树脂组合物，其特征在于，所述式(I)中，所述R 4为羟基或N-吗啉基。
  5. 根据权利要求4所述的固化性树脂组合物，其特征在于，所述A为氢或-CO-CR 2R 3R 4基团，且所述取代基-CO-CR 2R 3R 4基团中的R 2、R 3和R 4与权利要求1具有相同的定义。
  6. 根据权利要求1所述的固化性树脂组合物，其特征在于，所述第一光聚合引发剂(A1)和所述第二光聚合引发剂(A2)的重量比为(0.5～5)：(5～9.5)。
  7. 根据权利要求1至6中任一项所述的固化性树脂组合物，其特征在于，所述固化性树脂组合物还包括热固化性成分(D)，优选地，所述热固化性成分(D)选自封端异氰酸酯化合物、氨基树脂、马来酰亚胺化合物、苯并噁嗪树脂、碳二亚胺树脂、环碳酸酯化合物、多官能环氧化合物、多官能氧杂环丁烷化合物和环硫树脂组成的组中的一种或多种。
  8. 一种阻焊膜，其特征在于，所述阻焊膜采用权利要求1至7中任一项所述的固化性树脂组合物固化形成。
  9. 一种印刷电路板，包括阻焊膜，其特征在于，所述阻焊膜包括权利要求8所述的阻焊膜。
  10. 一种层间绝缘材料，其特征在于，所述层间绝缘材料采用权利要求1至7中任一项所述的固化性树脂组合物固化形成。
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CN101845216A (zh) * 2009-03-23 2010-09-29 太阳油墨制造株式会社 固化性树脂组合物、使用其的干膜和印刷电路板
CN101980081A (zh) * 2010-02-17 2011-02-23 太阳控股株式会社 阻焊剂组合物和印刷电路板
CN102944977A (zh) * 2012-11-28 2013-02-27 惠州市容大油墨有限公司 一种感光阻焊组合物、其用途及含有其的印刷电路板
JP2020169251A (ja) * 2019-04-02 2020-10-15 Ｄｉｃグラフィックス株式会社 活性エネルギー線硬化型インキ、インキ硬化物の製造方法及び印刷物

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