WO2021053773A1 - 感光性硬化性組成物、ドライフィルム、硬化物、および電子部品 - Google Patents

感光性硬化性組成物、ドライフィルム、硬化物、および電子部品 Download PDF

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WO2021053773A1
WO2021053773A1 PCT/JP2019/036648 JP2019036648W WO2021053773A1 WO 2021053773 A1 WO2021053773 A1 WO 2021053773A1 JP 2019036648 W JP2019036648 W JP 2019036648W WO 2021053773 A1 WO2021053773 A1 WO 2021053773A1
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compound
film
composition
curable composition
group
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PCT/JP2019/036648
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English (en)
French (fr)
Japanese (ja)
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亮 林
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太陽ホールディングス株式会社
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Priority to CN201980100113.XA priority Critical patent/CN114364717A/zh
Priority to PCT/JP2019/036648 priority patent/WO2021053773A1/ja
Priority to KR1020227007109A priority patent/KR20220064957A/ko
Priority to JP2021546122A priority patent/JP7420821B2/ja
Publication of WO2021053773A1 publication Critical patent/WO2021053773A1/ja

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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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • 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
    • G03F7/022—Quinonediazides
    • 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
    • G03F7/20—Exposure; Apparatus therefor

Definitions

  • the present invention relates to photosensitive curable compositions, dry films, cured products, and electronic components.
  • organic insulating materials are subjected to photolithography so that fine lines and openings can be formed with high precision in order to apply them to miniaturization of electronic components, high-definition design structures, and complicated manufacturing methods. It is also desired that pattern formation is possible.
  • such an organic insulating material forms a composition layer formed by applying the above composition on a film such as a PET film and drying it. Dry film-like products are also desired.
  • a main object of the present invention is to provide a photosensitive composition having excellent heat resistance (high Tg) and excellent dielectric properties (low dielectric constant and low dielectric loss tangent) and capable of forming a pattern by photolithography. To do.
  • Another object of the present invention is to provide a dry film having a composition layer obtained from the composition, a cured product of the composition or the composition layer of the dry film, and an electronic component having the cured product. It is in.
  • the present inventor has focused on the fact that the carbodiimide group undergoes a cross-linking reaction with a carboxyl group or a phenolic hydroxyl group at room temperature (about 25 ° C.) or higher, and that the carbodiimide group undergoes a self-crosslinking reaction at 180 ° C. or higher. Diligently examined for. As a result, they have found that the above problems can be solved by combining a compound having a carbodiimide group and a compound that generates a carboxyl group and / or a phenolic hydroxyl group by light, and complete the present invention. It came to.
  • the photosensitive curable composition of the present invention contains (A) a compound having a carbodiimide group, and (B) a compound that produces a carboxyl group and / or a phenolic hydroxyl group by light, preferably a naphthoquinonediazide compound. It is characterized by that.
  • the photosensitive curable composition of the present invention does not substantially contain a compound having a carboxyl group and / or a phenolic hydroxyl group in the composition.
  • the compound having the carbodiimide group (A) is blended in the organic component of the composition excluding the organic solvent in a proportion of 50 to 99% by mass.
  • the dry film of the present invention is characterized by comprising a composition layer obtained by applying and drying the photosensitive curable composition on a base material.
  • the cured product of the present invention is characterized in that the photosensitive curable composition or the composition layer of the dry film is cured.
  • the electronic component of the present invention is characterized by including the cured product.
  • a photosensitive curable composition having excellent heat resistance (high Tg) and excellent dielectric properties (low dielectric constant and low dielectric loss tangent) and capable of forming a pattern by photolithography. be able to. Further, according to the present invention, it is possible to provide a dry film having a composition layer obtained from the composition, a cured product of the composition or the composition layer of the dry film, and an electronic component having the cured product. ..
  • the photosensitive curable composition of the present invention is a composition containing (A) a compound having a carbodiimide group and (B) a compound that produces a carboxyl group and / or a phenolic hydroxyl group by light, and contains the carboxyl group and / Or it is preferable that the compound having a phenolic hydroxyl group is substantially not contained in the composition.
  • the fact that the composition does not substantially contain a compound having a carboxyl group and / or a phenolic hydroxyl group means that the carboxyl group and / or phenolic hydroxyl group equivalent of all the organic components of the composition excluding the organic solvent is 1. It means that it is 5,000 g / eq or more, preferably 5,000 g / eq or more. Within this range, excellent storage stability can be obtained.
  • the photosensitive curable composition of the present invention contains (A) a compound having a carbodiimide group.
  • the carbodiimide group contained in such a molecular structure undergoes a cross-linking reaction with a carboxyl group at room temperature (about 25 ° C.) or higher to form an N-acylurea bond, and a cross-linking reaction with a phenolic hydroxyl group at room temperature (about 25 ° C.) or higher.
  • a cross-linking reaction with an amino group at 150 ° C. or higher to form a guanidine bond a cross-linking reaction with an epoxy group at 150 ° C. or higher to form an imidazolidione ring bond, and 180 ° C. or higher.
  • the carbodiimide group undergoes a self-crosslinking reaction to form a triazine ring bond.
  • the cured product having the imidazolidione ring bond and the triazine ring bond formed exhibits excellent dielectric properties (low dielectric constant and low dielectric loss tangent) and excellent heat resistance (high glass transition temperature).
  • the composition does not substantially contain a compound having a carboxyl group and / or a phenolic hydroxyl group
  • the carbodiimide group and the carboxyl group or the phenolic hydroxyl group in the compound (A) are substantially not contained.
  • the cross-linking reaction caused by the reaction with is less likely to occur at room temperature, and exhibits excellent storage stability.
  • Examples of the diisocyanate used for synthesizing such a compound having a carbodiimide group (A) include aromatic diisocyanates, aliphatic diisocyanates, and alicyclic diisocyanates. Specifically, 1,5-naphthylene diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 1,3-phenylenediisocyanate, 1,4- Aromatic diisocyanates such as phenylenediocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, o-xylylene diisocyanate, m-xylylene diisocyanate, tetramethylxylylene diisocyanate, methylene diisocyanate, tetramethylene diisocyanate, he
  • Aliphatic diisocyanates such as methylene diisocyanate and trimethylhexamethylene diisocyanate, cyclohexane-1,4-diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, methylcyclohexanediisocyanate, 2,5-bis (isocyanatomethyl) bicyclo [ 2.2.1] Heptan, 2,6-bis (isocyanatomethyl) bicyclo [2.2.1] Heptan and other alicyclic diisocyanates and the like can be mentioned.
  • diisocyanates may be used alone or in combination of two or more, and from the viewpoint of reactivity and heat resistance as a cured product, they are soluble in aromatic diisocyanates and organic solvents, and have low flexibility as a cured product. From the viewpoint of dielectric properties, aliphatic diisocyanates and alicyclic diisocyanates can be appropriately used.
  • the compound having a carbodiimide group (A) used in the present invention has properties such as solubility in an organic solvent, storage stability, reactivity, and heat resistance of a cured product in a well-balanced manner.
  • a compound obtained by condensation polymerization of'-diphenylmethane diisocyanate and 4,4'-diphenylmethane diisocyanate in combination is preferable.
  • the compound having a carbodiimide group (A) thus obtained has a terminal isocyanate group, and the terminal isocyanate group deteriorates storage stability when an alcoholic hydroxyl group is present in the composition.
  • the compound that reacts with this isocyanate group include monoisocyanate, monoalcohol, monoamine, and acid anhydride.
  • Examples of the monoisocyanate include lower alkyl isocyanates such as methyl isocyanate, ethyl isocyanate, propyl isocyanate, n-, sec- or tert-butyl isocyanate, alicyclic aliphatic isocyanates such as cyclohexyl isocyanate, phenyl isocyanate, tolyl isocyanate and dimethyl.
  • Examples thereof include aromatic isocyanates such as phenylisocyanate and 2,6-diisopropylphenylisocyanate.
  • Examples of the monoalcohol include methanol, ethanol, cyclohexanol, polyethylene glycol monomethyl ether, polypropylene glycol monomethyl ether and the like.
  • Examples of the monoamine include primary amines such as butylamine and cyclohexylamine, and secondary amines such as diethylamine, dibutylamine and dicyclohexylamine.
  • Examples of the acid anhydride include phthalic anhydride, acetic anhydride, succinic anhydride, maleic anhydride, benzoic anhydride and the like. These may be used alone or in combination of two or more. Of these, phenylisocyanate and tolylisocyanate are preferable, and phenylisocyanate is more preferable, from the viewpoint of reactivity.
  • Such a compound having a carbodiimide group (A) can be used alone or in combination of two or more. Further, this compound having a carbodiimide group undergoes a self-crosslinking reaction (formation of a triazine ring bond) by blending an organic metal complex such as an organic cobalt complex or an organic manganese complex described later or a curing accelerator such as an organic metal salt. It can be promoted and imparted to low temperature curability.
  • the compound having a carbodiimide group constituting the photosensitive curable composition of the present invention has solubility in an organic solvent as a compound having a carbodiimide group, storage stability, and an exposed portion as a photosensitive curable composition.
  • the weight average molecular weight (Mw) is preferably 1,000 to 10,000, and more preferably 1,500 to 5,000. preferable.
  • the weight average molecular weight is a value measured by gel permeation chromatography (GPC) and converted into standard polystyrene.
  • the compound having a carbodiimide group (A) preferably has a carbodiimide group equivalent (g / eq) of 100 to 500, more preferably 150 to 350, from the viewpoint of reactivity. Further, the compound (A) having a carbodiimide group is preferably blended in a proportion of 50 to 99% by mass in all the organic components of the composition excluding the organic solvent. By blending in this range, a cured product having excellent dielectric properties and heat resistance can be obtained.
  • the photosensitive curable composition of the present invention contains (B) a compound that produces a carboxyl group and / or a phenolic hydroxyl group by light, preferably a naphthoquinone diazide compound.
  • This compound (B) is a compound that generates a carboxyl group and / or a phenolic hydroxyl group by light irradiation (exposure), and in an unexposed state, a functional group that causes a cross-linking reaction with a carbodiimide group in the compound (A). Does not generate.
  • the dry coating film made of the photosensitive curable composition of the present invention when patterned-exposed, it has a carboxyl group and / or a phenolic hydroxyl group generated from the compound (B) in the exposed portion and a (A) carbodiimide group.
  • the carbodiimide group of the compound undergoes a cross-linking reaction at room temperature (about 25 ° C.) or higher, the exposed portion is no longer dissolved in the developing solution, and a coating pattern is formed due to the difference in developability from the unexposed portion. ..
  • a known and commonly used compound can be used, but a naphthoquinone diazide compound that generates a carboxyl group by light is particularly preferable.
  • the naphthoquinone diazide compound include a naphthoquinone diazide adduct of tetrahydroxybenzophenone (for example, BS570 (adduct rate 70%), BS599 (adduct rate 99%) manufactured by Sanpo Chemical Laboratory Co., Ltd.) and 4- ⁇ 4-.
  • Phenol naphthoquinone diazide adduct for example, TKF-428 (adduct rate 93%), TKF-, manufactured by Sanpo Chemical Research Institute). 528 (addition rate 93%)) and the like. These may be used alone or in combination of two or more. Of these, a naphthoquinone diazide adduct of 4- ⁇ 4- [1,1-bis (4-hydroxyphenyl) ethyl] - ⁇ , ⁇ -dimethylbenzyl ⁇ phenol is preferable from the viewpoint of solubility in an organic solvent.
  • the above-mentioned naphthoquinone diazide compound has a possibility that the storage stability may be lowered because phenolic hydroxyl groups remain depending on the addition rate of naphthoquinone diazide. Therefore, the addition rate of naphthoquinonediazide is preferably 60% or more, more preferably 75% or more, and most preferably 80% or more so that the composition does not substantially contain a compound having a phenolic hydroxyl group. ..
  • the compound (B) that produces a carboxyl group and / or a phenolic hydroxyl group by light has a carbodiimide group of the compound (A) and a compound (B) in relation to the compound having the (A) carbodiimide group in the composition. It is preferable to mix them so that the equivalent ratio (carbodiimide group: carboxyl group and / or phenolic hydroxyl group) with the carboxyl group and / or phenolic hydroxyl group generated by exposure is 1: 0.01 to 0.2. It is more preferably 1: 0.02 to 0.1, and most preferably 1: 0.03 to 0.08.
  • the developer resistance of the exposed part can be obtained, and the carbodiimide group forms many crosslinked structures such as a triazine ring and an imidazolidione ring, and excellent dielectric properties and heat resistance can be obtained. Be done.
  • the photosensitive curable composition of the present invention may contain an organic compound that is liquid at 25 ° C. within a range that does not impair excellent dielectric properties and heat resistance. it can.
  • the organic compound which is liquid at 25 ° C., has the effect of lowering the softening point of the composition, improves the solubility of the developer in the unexposed portion, and at the time of cracking or cutting the composition layer of the dry film described later. It has a function of suppressing powder falling and improving the fluidity of the composition at the time of laminating, and the blending amount is preferably 10 to 40% by mass in the organic components of the composition excluding the organic solvent.
  • the organic compound having such a function and being liquid at 25 ° C. is not particularly limited as long as it does not substantially have a carboxyl group and / or a phenolic hydroxyl group. Of these, it is preferable to use an organic compound having a cyclic (thio) ether group and / or an ethylenically unsaturated bond.
  • Organic compound having a cyclic (thio) ether group that is liquid at 25 ° C.
  • organic compound having a cyclic (thio) ether group that is liquid at 25 ° C.
  • organic compound having a cyclic (thio) ether group that is liquid at 25 ° C.
  • Such a cyclic (thio) ether group undergoes a cross-linking reaction with a carbodiimide group at 150 ° C. or higher to form an imidazolidione ring or an imidazolidinethione ring bond.
  • the cured product having an imidazolidione ring or an imidazolidinethione ring bond formed has even more excellent dielectric properties (low dielectric constant and low dielectric loss tangent) and excellent heat resistance (high glass transition temperature). ..
  • organic compound having an epoxy group that is liquid at 25 ° C. known and commonly used ones can be used.
  • a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, and a bisphenol AF type epoxy resin can be used.
  • Dicyclopentadiene type epoxy resin trisphenol type epoxy resin, naphthol novolac type epoxy resin, phenol novolac type epoxy resin, alicyclic epoxy resin having an ester skeleton, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, Naftor type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin having a butadiene structure, alicyclic type Examples thereof include an epoxy resin, a heterocyclic epoxy resin, a spiro ring-containing epoxy resin, a cyclohexanedimethanol type epoxy resin, a naphthylene ether type epoxy resin, a trimethylol type epoxy resin, and a tetraphenylethane type epoxy resin.
  • the epoxy group (oxylan ring) of the organic compound having a liquid epoxy group is reacted with a sulfide agent such as thiourea to form an episulfide group (tyylan ring).
  • a sulfide agent such as thiourea
  • Examples of the organic compound having an oxetane group that is liquid at 25 ° C. include 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3- (phenoxymethyl) oxetane, and 3-ethyl-3- (2-ethylhexyloxymethyl).
  • Oxetane, 1,4-bis ⁇ [(3-ethyl-3-oxetanyl) methoxy] methyl ⁇ benzene, bis (3-ethyl-3-oxetanylmethyl) ether and the like can be mentioned.
  • Such an organic compound having a cyclic (thio) ether group that is liquid at 25 ° C. can be used alone or in combination of two or more.
  • the organic compound having a cyclic (thio) ether group can be imparted with low temperature curability by adding a curing accelerator such as imidazole, which will be described later. Further, known and commonly used effects derived from the molecular structure of an organic compound having a cyclic (thio) ether group are also effective in the present invention.
  • organic compound having an ethylenically unsaturated bond that is liquid at 25 ° C.
  • organic compound having an ethylenically unsaturated bond that is liquid at 25 ° C. include polyester (meth) acrylate, polyether (meth) acrylate, urethane (meth) acrylate, carbonate (meth) acrylate, and epoxy. Meta) acrylate and the like can be mentioned.
  • a radical polymerizable property by light irradiation (exposure) is imparted by using an organic compound having such an ethylenically unsaturated bond in combination with a photopolymerization initiator described later. Can be done.
  • organic compound having an ethylenically unsaturated bond that is liquid at 25 ° C. known and commonly used organic compounds can be used, for example, hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate, and ethylene glycol.
  • Diacrylates of glycols such as methoxytetraethylene glycol, polyethylene glycol, propylene glycol, acrylamides such as N, N-dimethylacrylamide, N-methylolacrylamide, N, N-dimethylaminopropylacrylamide, N, N-dimethylamino Aminoalkyl acrylates such as ethyl acrylate, N, N-dimethylaminopropyl acrylate, polyhydric alcohols such as hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, tris-hydroxyethyl isocyanurate or ethylene oxide adducts thereof.
  • glycols such as methoxytetraethylene glycol, polyethylene glycol, propylene glycol
  • acrylamides such as N, N-dimethylacrylamide, N-methylolacrylamide, N, N-dimethylaminopropylacrylamide
  • Polyvalent acrylates such as propylene oxide adducts or ⁇ -caprolactone adducts, polyvalent acrylates such as ethylene oxide adducts or propylene oxide adducts of bisphenol A, glycerin diglycidyl ethers, glycerin triglycidyl ethers, trimethylol
  • Polyvalent acrylates of glycidyl ethers such as propanetriglycidyl ether and triglycidyl isocyanurate, and not limited to the above, polyols such as polyether polyols, polycarbonate diols, hydroxyl group-terminated polybutadienes, and polyester polyols are directly acrylated or via diisocyanate.
  • Examples thereof include acrylates and melamine acrylates that have been converted to urethane acrylates, and methacrylates corresponding to the acrylates.
  • trimethylolpropane an ethylene oxide adduct of bisphenol A and / or a propylene oxide adduct are preferable because of their excellent flexibility and reactivity.
  • Such an organic compound having an ethylenically unsaturated bond that is liquid at 25 ° C. can be used alone or in combination of two or more.
  • Equipment Constant temperature water tank Use one equipped with a stirrer, heater, thermometer, and automatic temperature controller (those that can control the temperature at ⁇ 0.1 ° C) and have a depth of 150 mm or more.
  • Test tube As shown in FIG.
  • the test tube is made of flat-bottomed cylindrical transparent glass having an inner diameter of 30 mm and a height of 120 mm, and marked lines 11 and 12 at heights of 55 mm and 85 mm from the tube bottom, respectively.
  • the test tube 10a for liquid judgment which has the mouth of the test tube sealed with a rubber stopper 13a, is similarly marked with the same size and has a hole in the center for inserting and supporting the thermometer.
  • a temperature measurement test tube 10b is used in which the mouth of the test tube is sealed with a rubber stopper 13b and a thermometer 14 is inserted into the rubber stopper 13b.
  • the marked line 11 having a height of 55 mm from the bottom of the pipe is referred to as "line A”
  • the marked line 12 having a height of 85 mm from the bottom of the pipe is referred to as "line B”.
  • the thermometer 14 the one for freezing point measurement (SOP-58 scale range 20 to 50 ° C.) specified in JIS B7410 (1982) "Glass thermometer for petroleum test” is used, but the temperature is 0 to 50 ° C. Anything that can measure the range will do.
  • liquid judgment test tube 10a After 10 minutes, take out the liquid judgment test tube 10a from the low temperature constant temperature water tank, immediately lay it horizontally on a horizontal test table, and use a stopwatch to measure the time when the tip of the liquid level in the test tube moves from line A to line B. Measure and record. As for the sample, those having a measured time of 90 seconds or less at a set temperature are judged to be liquid, and those having a measured time of more than 90 seconds are judged to be solid.
  • the photosensitive curable composition of the present invention can further contain a curing accelerator.
  • the curing accelerator include 1,8-diazabicyclo [5.4.0] undecene-7, 1,5-diazabicyclo [4.3.0] nonen-5, 5,6-dibutylamino-1,8.
  • Cycloamidine compounds such as Undecene-7, dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine , 4-Methyl-N, N-Dimethylbenzylamine and other amine compounds, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1- Imidazole compounds such as cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole, 1-benzyl-2-phenylimidazole and derivatives thereof, tributylphosphine, methyldiphenylphosphine, triphenylphosphine
  • Organic phosphine compounds such as tris (4-methylphenyl) phosphine, diphenylphosphine, phenylphosphine, organic cobalt complexes such as cobalt (II) acetylacetonate, cobalt (III) acetylacetonate, copper (II) acetylacetonate, etc.
  • Organic copper complex organic zinc complex such as zinc (II) acetylacetonate, organic iron complex such as iron (III) acetylacetonate, organic nickel complex such as nickel (II) acetylacetonate, manganese (II) acetylacetate
  • organic metal complexes such as organic manganese complexes such as nat and organic metal salts. These may be used alone or in combination of two or more.
  • the photosensitive curable composition of the present invention can further contain a photopolymerization initiator.
  • the photopolymerization initiator include bis- (2,6-dichlorobenzoyl) phenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -2,5-dimethylphenylphosphine oxide, and bis- (2, 6-Dichlorobenzoyl) -4-propylphenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -1-naphthylphosphine oxide, bis- (2,6-dimethoxybenzoyl) phenylphosphine oxide, bis- (2,6-dimethoxybenzoyl) 2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,5-dimethylphen
  • Ketals such as anthraquinones, acetophenone dimethyl ketal, benzyl dimethyl ketal, benzoic acid esters such as ethyl-4-dimethylaminobenzoate, 2- (dimethylamino) ethyl benzoate, p-dimethylbenzoic acid ethyl ester, 1,2- Octandione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl]- , 1- (O-Acetyloxime) and other oxime esters, bis ( ⁇ 5-2,4-cyclopentadiene-1-yl) -bis (2,6-difluoro-3- (1H-pyrrole-1-yl)) Oxime) Titanium, bis (cyclopentadienyl) -bis [2,6-diflu
  • the blending amount thereof is 0.1 to 0.1 to that of the organic compound having an ethylenically unsaturated bond. It is preferably 10% by mass.
  • the photosensitive curable composition of the present invention can further contain an organic solvent.
  • an organic solvent it is preferable to select a solvent having excellent solubility in the compound having the (A) carbodiimide group, which is the main component of the composition (good solvent).
  • examples of such an organic solvent as a good solvent include alicyclic ethers such as tetrahydrofuran, 1,3-dioxane and dioxolane, aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene, chlorobenzene, dichlorobenzene and tri.
  • Examples thereof include halogenated hydrocarbons such as chlorobenzene, percrene, trichloroethane and dichloroethane, cyclohexanone and petroleum naphtha. Of these, cyclohexanone and petroleum naphtha are preferable from the viewpoint of low cost and low toxicity.
  • the petroleum naphtha heavy naphtha having a boiling point range of 80 to 180 ° C. is preferable, and commercially available products include Solvent # 100 and Solvent # 150 manufactured by Sankyo Chemical Co., Ltd., Solvent Naphtha, and Ipsol # 100 and Ipsol # manufactured by Idemitsu Showa Shell.
  • the photosensitive curable composition of the present invention can further contain an inorganic filler.
  • inorganic fillers can be used, for example, barium sulfate, barium titanate, amorphous silica, crystalline silica, molten silica, spherical silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide.
  • the shape of these inorganic fillers is preferably spherical because the filler, the fluidity of the composition, and the handling as a dry film are improved.
  • the main spherical inorganic filler and the main spherical filler are used. It is more preferable to combine a spherical inorganic filler having an average particle size of 1/5 to 1/50 with respect to the average particle size of the inorganic filler.
  • the average particle size of the inorganic filler can be appropriately selected in the range of 50 nm to 20 ⁇ m, and the light transmission during exposure and the pattern resolution are improved. Therefore, the average particle size is 50 nm to 2 ⁇ m.
  • the average particle size is preferably 1 ⁇ m to 20 ⁇ m because the filling property and the fluidity of the composition are improved.
  • the average particle size in the present invention is a value of D50 measured by a laser diffraction method. Examples of the measuring device by the laser diffraction method include the Microtrac MT3300EXII manufactured by Nikkiso Co., Ltd.
  • the inorganic filler is preferably surface-treated with a coupling agent or the like from the viewpoint of improving the dispersibility and filling property of the composition and improving the mechanical properties of the cured product.
  • a coupling agent include silane-based, titanate-based, aluminate-based, and zirco-aluminate-based coupling agents, and among them, the silane-based coupling agent is preferable.
  • the silane coupling agent include vinylsilanes such as vinyltrimethoxysilane and vinyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and 2- (3,4-).
  • Epoxycyclohexyl Epoxysilanes such as ethyltrimethoxysilane, methacrylsilanes such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, acrylic silanes such as 3-acryloxypropyltrimethoxysilane, 3-mercapto Mercaptosilane such as propyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-phenyl-3-amino Examples thereof include aminosilanes such as propyltrimethoxysilane and alkoxysilanes such as phenyltrimethoxysilane.
  • vinylsilanes, epoxysilanes, methacrylsilanes, and phenyltrimethoxysilanes are preferable because they improve the dispersibility of the inorganic filler in the composition and are excellent in storage stability.
  • vinylsilanes, methacrylsilanes, and acrylicsilanes are more preferable because radical polymerizable properties can be obtained by using them in combination with the above-mentioned photopolymerization initiator, and the developer resistance of the exposed portion can be improved.
  • Inorganic fillers to which an organic functional group has been added by surface treatment with such a coupling agent or the like are treated as non-organic components in the present specification.
  • heat resistance and chemical resistance derived from barium sulfate, low thermal expansion and low dielectric normal contact derived from silica, flame retardancy imparted from aluminum hydroxide and magnesium hydroxide, alumina, and silicon nitride examples thereof include imparting thermal conductivity derived from silicon, boron nitride and aluminum nitride, roughening the surface of a cured product derived from calcium carbonate, and imparting conductivity derived from silver powder, copper powder and solder powder.
  • the blending amount of the inorganic filler is preferably 20 to 93% by mass with respect to the total amount of the components of the photosensitive curable composition excluding the organic solvent. This blending amount is appropriately adjusted according to the purpose of use of the composition, and is 20 to 75% by mass for applications such as protective films for printed wiring boards and semiconductor elements, electrically insulating layers, and adhesive layers for fixing electronic components. Is preferable, and 60 to 93% by mass is preferable for applications such as a sealing material for sealing or incorporating an electronic component, a component-embedded layer, or a molded product material.
  • the photosensitive curable composition according to the present invention may contain other components other than the above-mentioned components, for example, known and commonly used additives, as long as the effects of the present invention are not impaired.
  • known and commonly used additives are not particularly limited, and examples thereof include resins and elastomers, colorants, flame retardants, dispersants, defoamers / leveling agents, and rocking agents.
  • the resin and elastomer examples include epoxy resin, benzoxazine resin, imide resin, maleimide resin, amide resin, unsaturated polyester resin, acrylate resin, diallyl phthalate resin, silicone resin, norbornene resin, isocyanate resin, which are not liquid at 25 ° C.
  • examples thereof include urethane resin, benzocyclobutene resin, polyazomethine resin, block copolymer, natural rubber, diene rubber, non-diene rubber, and thermoplastic elastomer.
  • colorant examples include those having a color index (issued by The Society of Dyers and Colorists) as a color pigment, a dye, or the like.
  • examples of the red colorant include monoazo, disazo, azolake, benzimidazolone, perylene, diketopyrrolopyrrole, condensed azo, anthraquinone, and quinacridone.
  • examples of the blue colorant include phthalocyanine type and anthraquinone type, and as the pigment type, a compound classified as Pigment can be used. In addition to these, metal-substituted or unsubstituted phthalocyanine compounds can also be used.
  • the green colorant there are phthalocyanine type, anthraquinone type, and perylene type.
  • metal-substituted or unsubstituted phthalocyanine compounds can also be used.
  • the yellow colorant include monoazo, disazo, condensed azo, benzimidazolone, isoindolinone, anthraquinone and the like.
  • the white colorant include rutile-type or anatase-type titanium oxide.
  • Black colorants include carbon black, graphite, iron oxide, titanium black, iron oxide, anthraquinone, cobalt oxide, copper oxide, manganese, antimony oxide, nickel oxide, perylene, and aniline.
  • a colorant such as purple, orange, or brown may be added for the purpose of adjusting the color tone.
  • Dispersant examples include high molecular weight dispersants such as polycarboxylic acid type, naphthalene sulfonic acid formalin condensation type, polyethylene glycol, polycarboxylic acid partial alkyl ester type, polyether type, and polyalkylene polyamine type, alkyl sulfonic acid type, and four. Examples thereof include low molecular weight dispersants such as higher ammonium type, higher alcohol alkylene oxide type, polyhydric alcohol ester type, and alkyl polyamine type, which improve the dispersibility of each component in the composition and further improve the mechanical properties of the cured product. Can be improved.
  • high molecular weight dispersants such as polycarboxylic acid type, naphthalene sulfonic acid formalin condensation type, polyethylene glycol, polycarboxylic acid partial alkyl ester type, polyether type, and polyalkylene polyamine type, alkyl sulfonic acid type, and four.
  • low molecular weight dispersants such as higher am
  • Defoamer / leveling agent Compounds such as silicone, modified silicone, mineral oil, vegetable oil, fatty alcohol, fatty acid, metal soap, fatty acid amide, polyoxyalkylene glycol, polyoxyalkylene alkyl ether, and polyoxyalkylene fatty acid ester are used as antifoaming agents and leveling agents. Etc. can be used, the smoothness of the surface of the coating film is improved, and the generation of voids in the coating film can be suppressed.
  • rocking agent fine particle silica gel, silica gel, amorphous inorganic particles, polyamide-based additive, modified urea-based additive, wax-based additive, organic bentonite, etc. can be used, which improves the film-forming property of the coating film and causes sagging. Can be suppressed.
  • Flame retardants include red phosphorus, ammonium phosphate, ammonium carbonate, zinc borate, zinc tinate, molybdenum compound, bromine compound, chlorine compound, phosphoric acid ester, phosphorus-containing polyol, phosphorus-containing amine, melamine cyanurate, and melamine.
  • Compounds, triazine compounds, guanidine compounds, silicone polymers and the like can be used, and self-extinguishing properties and heat resistance of cured products can be achieved at a high level in a well-balanced manner.
  • the dry film of the present invention has a composition layer obtained by applying the photosensitive curable composition of the present invention on a base material (for example, a support (carrier) film) and then drying the film. Then, this composition layer is thermocompression-bonded (laminated) so as to be in contact with another target base material.
  • a base material for example, a support (carrier) film
  • the dry film of the present invention has a photosensitive curable composition of the present invention on a substrate (for example, a support (carrier) film) by an appropriate method such as a blade coater, a lip coater, a comma coater, or a film coater. It can be produced by uniformly applying the material and drying it to form a composition layer, preferably by laminating a film (so-called protective (cover) film) on the composition layer.
  • the protective film and the support film may be the same film material or different films may be used.
  • the film material of the support film and the protective film known and commonly used films used for the dry film can be used.
  • the support film for example, a thermoplastic film such as a polyester film such as polyethylene terephthalate having a thickness of 2 to 150 ⁇ m is used.
  • a support film having excellent light transmission and a support film having a roughened surface in contact with the composition layer are used to form a rough surface shape of the support film on the surface of the composition layer.
  • a transfer technique can be used.
  • the protective film a polyethylene film, a polypropylene film, or the like can be used, but it is preferable that the protective film has a smaller adhesive force with the composition layer than the support film.
  • the film thickness of the composition layer of the dry film of the present invention is preferably 1 to 40 ⁇ m, more preferably 1 to 30 ⁇ m.
  • nitrogen gas generated especially from the naphthoquinone diazide compound is removed from the composition layer when irradiated with light or heated, and a good coating film and a cured film are formed. be able to.
  • the composition layer made of the photosensitive curable composition of the present invention is used as a protective layer (outer layer), and the compound (B) such as the naphthoquinone diazide compound is removed from the photosensitive curable composition of the present invention.
  • a dry film having a two-layer structure can be obtained by using the curable composition as an adhesive layer (inner layer). According to such a two-layer structure, the exposed portion of the protective layer prevents the adhesive layer immediately below from melting during development, and the pattern can be formed in the two-layer structure.
  • the film thickness of the protective layer is preferably 1 to 40 ⁇ m, more preferably 1 to 30 ⁇ m, and the film thickness of the adhesive layer is preferably 1 to 100 ⁇ m.
  • the photosensitive curable composition of the present invention is applied onto a support film and dried to form a protective layer, and then the protective layer is formed.
  • a curable composition obtained by removing the compound (B) such as a naphthoquinone diazide compound from the photosensitive curable composition of the present invention is applied onto the film and dried to form an adhesive layer, and then, if necessary, on the adhesive layer. It is manufactured by laminating a protective film on the surface.
  • the photosensitive curable composition of the present invention is applied onto a support film and dried, and the protective film is covered with a naphthoquinone diazide compound or the like from the photosensitive curable composition of the present invention.
  • a curable composition excluding compound (B) is applied to prepare a dry adhesive layer, and the protective layer and the adhesive layer are laminated so as to be in contact with each other.
  • the method of using the two-layer structure dry film is to peel off the protective film on the adhesive layer side and thermocompression-bond (laminate) the adhesive layer so that it is in contact with another target base material, and then the manufacturing process. Is the same as when a single-layer dry film is used.
  • the cured product of the present invention is a cured product of the above-mentioned photosensitive curable composition of the present invention or the composition layer of a dry film.
  • Examples of the method for obtaining the photosensitive curable composition of the present invention or the cured product in which a pattern is formed using the dry film on which the composition layer is formed include a method through the following steps.
  • a dry coating film is formed by applying and drying a photosensitive curable composition on a substrate, or by transferring a composition layer from a dry film.
  • this coating film forming step as a method of applying the photosensitive curable composition on the substrate, conventional coating methods such as a spin coater, a bar coater, a blade coater, a curtain coater, and a screen printing machine are used.
  • a method of coating with a spray coater, a method of spray coating with a spray coater, an inkjet method, or the like can be used.
  • a method for drying the coating film a method such as heating and drying with an oven or a hot plate is used.
  • the coating film is dried under conditions that do not cause a thermal reaction of the compound (B) in the photosensitive curable composition.
  • the condition is 110 ° C. or lower for 1 to 30 minutes, preferably 90 ° C. or lower for 1 to 30 minutes.
  • the base material used in this step is not particularly limited as long as it is a base material resistant to a curing temperature of 180 ° C. or higher, and is a base material cured by impregnating a semiconductor base material such as a silicon wafer or glass fiber with a curable resin. It can be widely applied to a printed wiring board in which a circuit such as copper is formed in advance on a material or a polyimide film, a wiring board such as a flexible printed wiring board, a metal substrate, or the like.
  • the dry coating film formed on the substrate in the above step is exposed to a pattern by irradiating it with active energy rays through a photomask having a pattern or directly.
  • the support film can be peeled off and then exposed, or the support film can be peeled off after being exposed on the support film.
  • the active energy ray one having a wavelength capable of activating the compound (B) is used.
  • a device equipped with a high-pressure mercury lamp, a metal halide lamp, or the like and irradiating ultraviolet rays in the range of 350 to 450 nm may be used for direct drawing (direct).
  • An imaging exposure) device can also be used.
  • the exposure amount varies depending on the film thickness and the like, but is generally in the range of 10 to 1000 mJ / cm 2.
  • PEB POST EXPOSURE BAKE
  • This PEB step is a step of accelerating the reaction between the carboxyl group and / or the phenolic hydroxyl group generated from the compound (B) by exposure and the carbodiimide group by heating.
  • the reaction between the carboxyl group and / or the phenolic hydroxyl group and the carbodiimide group proceeds even at about 25 ° C., but the pattern formation property is improved by performing PEB.
  • a method such as heating with an oven or a hot plate is used.
  • this PEB step is performed at a temperature under conditions under which the thermal reaction of the compound (B) such as the naphthoquinone diazide compound in the unexposed portion does not occur. Specifically, it is preferably 110 ° C. or lower for 1 to 30 minutes, and 90 ° C. or lower for 1 to 30 minutes.
  • the dry coating film after the exposure step or the PEB step is treated with a developing solution. Thereby, the unexposed portion in the coating film can be removed to form the pattern film of the photosensitive curable composition of the present invention.
  • an arbitrary method is selected from conventionally known photolithography developing methods such as a rotary spray method, a paddle method, and a dipping method accompanied by ultrasonic treatment. Can be done.
  • the developing solution the above-mentioned organic solvent can be used, and among them, petroleum naphtha or a developing solution in which petroleum naphtha and cyclohexanone are combined is preferable.
  • the higher the ratio of cyclohexanone the better the developability of the unexposed portion, and the higher the ratio of petroleum naphtha, the more the development damage in the exposed portion is suppressed.
  • the mixing ratio of petroleum naphtha and cyclohexanone is preferably 9.5: 0.5 to 5: 5, and more preferably 9: 1 to 7: 3. Further, if necessary, an appropriate amount of a surfactant may be added to the developing solution.
  • the temperature of the developing solution is 20 to 40 ° C., and the developing time is 180 seconds or less.
  • the obtained pattern film is washed with a rinsing solution. Distilled water, methanol, ethanol, isopropyl alcohol and the like can be used alone or in combination as the rinsing solution.
  • the pattern film obtained in the above developing step is subjected to a denitrification step as necessary.
  • the denitrification method can be carried out by heating the coating film.
  • the naphthoquinone diazide compound as compound (B) can be inactivated by reacting the unphotosensitive naphthoquinone diazide compound remaining in the exposed portion with heat.
  • a heating method in the denitrification step a method such as heating with an oven or a hot plate can be mentioned.
  • the heating conditions are 120 to 140 ° C. for 1 to 30 minutes. In such a temperature range, the naphthoquinone diazide compound undergoes a complete thermal reaction to release nitrogen, and the curing reaction of the pattern film does not proceed easily. Therefore, the generated nitrogen is removed without remaining in the coating film. Will be done.
  • the patterned film that has completed the developing step or the denitrification step is heated as a curing step to obtain a cured coating film (cured product).
  • the carbodiimide group undergoes a cross-linking reaction and is cured.
  • the heating conditions in this curing step are 180 to 250 ° C. for 30 to 90 minutes, but when the composition contains a compound having a cyclic (thio) ether group, before the heating conditions. Heating at 150-170 ° C. for 30-90 minutes may be applied.
  • the photosensitive curable composition or dry film of the present invention seals or encloses a protective film such as a printed wiring board or a semiconductor element, an electrically insulating layer, an electronic component, etc. It can be used for adhesive layers, etc., and in particular, high-density wiring that requires low dielectric constant and low dielectric loss tangent, electronic components that handle high-frequency signals, and electronics for automobiles and robots that require high temperature and long-term reliability. Suitable for parts.
  • the obtained compound (A1) having a carbodiimide group had a weight average molecular weight of 2,100 and a carbodiimide group equivalent of 205 g / eq.
  • Spherical silica surface treatment Spherical silica surface treatment
  • Spherical silica (Admatex) is a mixture of 50 parts by mass of PMA (propylene glycol monomethyl ether acetate) and 3 parts by mass of acrylic silane coupling agent (KBM-5103 (3-acryloxypropyltrimethoxysilane) manufactured by Shinetsu Silicone). , SO-E2, average particle size 0.5 ⁇ m) 100 parts by mass was added, stirred and uniformly dispersed, and then heat-dried to obtain surface-treated spherical silica.
  • PMA propylene glycol monomethyl ether acetate
  • acrylic silane coupling agent KBM-5103 (3-acryloxypropyltrimethoxysilane) manufactured by Shinetsu Silicone
  • the spherical silica is 100 parts by volume of spherical alumina (Admatex, A-509, average particle diameter of 10 ⁇ m), and the coupling agent is an epoxysilane-based coupling agent (KBM-403 (3-) manufactured by Shinetsu Silicone). Glycydoxypropyltrimethoxysilane)) Surface-treated spherical alumina was obtained in the same manner as the surface treatment of silica except that it was changed to 3 parts by mass.
  • Examples 1 to 13, Comparative Example 1 According to the formulation shown in Table 1 below, each component is blended, stirred with a stirrer, and kneaded with a three-roll mill as necessary to prepare the photosensitive curable compositions of Examples 1 to 13 and Comparative Example 1. did.
  • the blending amount in the table indicates a part by mass.
  • the obtained photosensitive curable compositions of Examples and Comparative Examples were applied onto a copper plate with an applicator so that the coating film thickness after drying was about 25 ⁇ m as a coating film forming step, and then placed in an oven. It was dried at 80 ° C. for 30 minutes.
  • a photomask having a line pattern of 100 ⁇ m is brought into close contact with the obtained dry coating film, and exposure (exposure amount) is performed using an ultraviolet exposure device (manufactured by ORC Manufacturing Co., Ltd., model HMW-680GW). 1 J / cm 2 ).
  • the exposed coating film was heat-treated in an oven at 80 ° C. for 30 minutes.
  • the dry coating film having completed the PEB step is immersed in a developing solution containing 90% by mass of petroleum naphtha (Cactus Fine SF-01) and 10% by mass of cyclohexanone at 20 ° C. for 60 seconds and shaken.
  • a copper plate (test piece) having a patterned coating film (pattern film) was produced.
  • the residual state of the line was visually measured, the film thickness after development was measured with a micrometer, and the pattern formability was evaluated according to the following evaluation criteria. The results are shown in Table 1.
  • ⁇ There is no line defect, and the difference between the film thickness before drying and the film thickness after development is less than 2 ⁇ m.
  • ⁇ The line is partially defective, or the difference between the film thickness before drying and the film thickness after development is 2 ⁇ m or more.
  • Pattern formation is impossible
  • the dry coating film having completed the PEB step is immersed in a developing solution containing 90% by mass of petroleum naphtha (Cactus Fine SF-01) and 10% by mass of cyclohexanone at 20 ° C. for 60 seconds and shaken. It was developed while letting it.
  • a denitrification step the obtained coating film is heated in an oven at 130 ° C. for 30 minutes, and further, as a curing step, the temperature is raised to 250 ° C. and heat treatment is performed for 60 minutes, and a test in which a cured film is provided on the copper foil. Pieces were made.
  • Comparative Example 1 since pattern formation was not possible in the above-mentioned test, a test piece was prepared except for the above-mentioned developing step.
  • the cured film of the test piece thus produced is peeled off from the copper foil, and the dielectric constant and dielectric loss tangent at 10 GHz are measured using an SPDR dielectric resonator and a network analyzer (both manufactured by Agilent) as a cured film sample. Then, each evaluation was made according to the following evaluation criteria. The results are shown in Table 1. (Evaluation criteria for permittivity) ⁇ : less than 3.3 ⁇ : 3.3 or more and less than 3.5 ⁇ : 3.5 or more (evaluation standard for dielectric loss tangent) ⁇ : less than 0.015 ⁇ : 0.015 or more and less than 0.02 ⁇ : 0.02 or more
  • the photosensitive curable composition of Example 11 was applied onto a PET film (manufactured by Toray Industries, Inc., Lumirror T60, thickness 25 ⁇ m) with an applicator so that the coating thickness after drying was 20 ⁇ m, and 80 in an oven.
  • the film was dried at ° C. for 30 minutes to prepare a dry film A having a composition layer composed of the photosensitive curable composition of Example 12 shown in Table 2 as a single layer.
  • a composition obtained by removing the naphthoquinone diazide compound from the photosensitive curable composition of Example 12 was prepared, and the composition was further dried on the composition layer of the dry film A with an applicator.
  • a dry film B having a two-layer structure having a certain protective layer and an adhesive layer was produced.
  • the dry films A and B thus produced were placed on a copper plate so that the PET film was on the outside, and a vacuum laminator (CVP-300 manufactured by Nikko Materials) was used to apply pressure: 0.4 MPa, 110 ° C.
  • the film was heat-laminated for 1 minute under the condition of vacuum degree: 3 hPa.
  • the PET film was peeled off to prepare a test piece having a patterned coating film and a test piece having a patterned cured film by the same method as the above-mentioned evaluation test for pattern forming property and appearance of cured product. , The pattern forming property and the appearance of the cured product were evaluated. The results are shown in Table 2.
  • the photosensitive curable composition of the present invention can be made into a single-layer dry film or a two-layer structure dry film, and according to these dry films. It was confirmed that the pattern was formed by photolithography, there were no abnormalities such as voids in the appearance, and a cured product of a thick film could be obtained.

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