WO2021053773A1 - Photosensitive curable composition, dry film, cured product, and electronic component - Google Patents

Photosensitive curable composition, dry film, cured product, and electronic component Download PDF

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Publication number
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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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 JP2021546122A priority Critical patent/JP7420821B2/en
Priority to CN201980100113.XA priority patent/CN114364717A/en
Priority to KR1020227007109A priority patent/KR20220064957A/en
Priority to PCT/JP2019/036648 priority patent/WO2021053773A1/en
Publication of WO2021053773A1 publication Critical patent/WO2021053773A1/en

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • 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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Abstract

The present invention addresses the problem of providing: a photosensitive curable composition that has superior heat resistance (high Tg) and dielectric properties (low permittivity and low dielectric tangent), and can be patterned by photolithography; a dry film comprising a composition layer obtained from said composition; a cured product of the composition or the composition layer of the dry film; and an electronic component comprising the cured product. The means for solving this problem is a photosensitive curable composition characterized by containing (A) a compound comprising a carbodiimide group, and (B) a compound that generates carboxyl groups and/or phenolic hydroxy groups when irradiated with light.

Description

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Photosensitive curable compositions, dry films, cured products, and electronic components
　本発明は、感光性硬化性組成物、ドライフィルム、硬化物、および電子部品に関する。 The present invention relates to photosensitive curable compositions, dry films, cured products, and electronic components.
　近年、自動車の分野では、自動車の省エネと自動運転化のため、燃料調整やブレーキ機能制御、ギヤ制御など、電子制御化の検討が盛んに行われている。このような自動車の電子制御化に伴い、自動車に組み込まれる電子部品には、２００℃を超える高温下での長期間の信頼性が要求されており、かかる電子部品に用いられる有機絶縁材料には、優れた耐熱性が望まれている。 In recent years, in the field of automobiles, in order to save energy and automate driving of automobiles, studies on electronic control such as fuel adjustment, brake function control, and gear control are being actively conducted. With such electronic control of automobiles, electronic parts incorporated in automobiles are required to have long-term reliability at high temperatures exceeding 200 ° C., and organic insulating materials used for such electronic parts are required. , Excellent heat resistance is desired.
　また、コンピューターや情報通信機器の分野では、電子部品の更なる高性能・高機能化が進み、大量のデータを高速で処理するため、扱う電気信号が高周波数化する傾向にある。このような高周波数化した電気信号を扱う電子部品では、伝送損失を抑制することが重要であり、かかる電子部品に用いられる有機絶縁材料には、低誘電率及び低誘電正接といった優れた誘電特性も望まれている。 Also, in the fields of computers and information and communication equipment, electronic components are becoming more sophisticated and functional, and in order to process a large amount of data at high speed, the frequency of electrical signals handled tends to increase. It is important to suppress transmission loss in electronic components that handle such high-frequency electrical signals, and the organic insulating material used in such electronic components has excellent dielectric properties such as low dielectric constant and low dielectric loss tangent. Is also desired.
　さらに、このような有機絶縁材料には、電子部品の小型化、高精細な設計構造、複雑な製造方法に適用するために、微細なラインや開口部を高精度で形成できるようにフォトリソグラフィによるパターン形成が可能であることも望まれている。 Furthermore, such 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.
　さらにまた、このような有機絶縁材料には、膜厚の制御や工程の簡便化といった観点から、ＰＥＴフィルム等のフィルム上に、上述の組成物を塗布し乾燥させてなる、組成物層を形成したドライフィルム状の製品も望まれている。 Furthermore, from the viewpoint of controlling the film thickness and simplifying the process, 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.
　これに対し従来、優れた耐熱性や低誘電率および低誘電正接を有する有機絶縁材料として、例えば、特許文献１のようなカルボジイミド化合物を含む樹脂組成物が開示されている。 On the other hand, conventionally, as an organic insulating material having excellent heat resistance, low dielectric constant and low dielectric loss tangent, for example, a resin composition containing a carbodiimide compound as in Patent Document 1 has been disclosed.
特開２０１７－１７９３０７号公報Japanese Unexamined Patent Publication No. 2017-179307
　しかしながら、特許文献１に開示された組成物の硬化物は、上述した２００℃を超える耐熱性、優れた誘電特性（低誘電率および低誘電正接）を備えるものの、フォトリソグラフィによるパターン形成の要求を満足し得るものではなかった。 However, although the cured product of the composition disclosed in Patent Document 1 has the above-mentioned heat resistance exceeding 200 ° C. and excellent dielectric properties (low dielectric constant and low dielectric loss tangent), there is a demand for pattern formation by photolithography. I wasn't satisfied.
　そこで、本発明の主たる目的は、優れた耐熱性（高Ｔｇ）、かつ優れた誘電特性（低誘電率および低誘電正接）を有し、フォトリソグラフィによるパターン形成が可能な感光性組成物を提供することにある。
　また、本発明の他の目的は、該組成物から得られる組成物層を有するドライフィルム、該組成物または該ドライフィルムの組成物層の硬化物、該硬化物を有する電子部品を提供することにある。 Therefore, 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.
　本発明者は、カルボジイミド基が常温（約２５℃）以上でカルボキシル基またはフェノール性水酸基と架橋反応すること、また、カルボジイミド基が１８０℃以上で自己架橋反応することに着目し、上記目的の実現に向け鋭意検討を行った。その結果、カルボジイミド基を有する化合物と、光によってカルボキシル基および／またはフェノール性水酸基を生成する化合物とを組み合わせた組成物とすることにより、上記課題を解決しうることを見出し、本発明を完成するに至った。 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.
　すなわち、本発明の感光性硬化性組成物は、（Ａ）カルボジイミド基を有する化合物と、（Ｂ）光によってカルボキシル基および／またはフェノール性水酸基を生成する化合物、好ましくはナフトキノンジアジド化合物と、を含むことを特徴とするものである。 That is, 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.
　本発明の感光性硬化性組成物は、組成物中にカルボキシル基および／またはフェノール性水酸基を有する化合物を実質的に含まないことが好ましい。 It is preferable 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.
　本発明の感光性硬化性組成物は、前記（Ａ）カルボジイミド基を有する化合物が、有機溶剤を除く組成物の有機成分中に５０～９９質量％の割合で配合されていることが好ましい。 In the photosensitive curable composition of the present invention, it is preferable that 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.
　本発明のドライフィルムは、基材上に、前記感光性硬化性組成物を塗布、乾燥してなる組成物層を備えることを特徴とするものである。 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.
　本発明の硬化物は、前記感光性硬化性組成物または前記ドライフィルムの組成物層を硬化してなることを特徴とするものである。 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.
　本発明の電子部品は、前記硬化物を備えることを特徴とするものである。 The electronic component of the present invention is characterized by including the cured product.
　本発明によれば、優れた耐熱性（高Ｔｇ）、かつ優れた誘電特性（低誘電率及び低誘電正接）を有し、フォトリソグラフィによるパターン形成が可能な感光性硬化性組成物を提供することができる。
　また、本発明によれば、該組成物から得られる組成物層を有するドライフィルム、該組成物または該ドライフィルムの組成物層の硬化物、該硬化物を有する電子部品を提供することができる。 According to the present invention, there is provided 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. ..
液状判定に用いる２本の試験管の概略側面図である。It is a schematic side view of two test tubes used for liquidity determination.
　以下、本発明の感光性硬化性組成物が含有する成分について詳述する。 Hereinafter, the components contained in the photosensitive curable composition of the present invention will be described in detail.
＜感光性硬化性組成物＞
　本発明の感光性硬化性組成物は、（Ａ）カルボジイミド基を有する化合物と、（Ｂ）光によってカルボキシル基および／またはフェノール性水酸基を生成する化合物と、を含む組成物であり、カルボキシル基および／またはフェノール性水酸基を有する化合物は組成物中に実質的に含まないことが好ましい。
　本発明において、組成物中にカルボキシル基および／またはフェノール性水酸基を有する化合物を実質的に含まないとは、有機溶剤を除く組成物の全有機成分のカルボキシル基および／またはフェノール性水酸基当量が１，０００ｇ／ｅｑ以上、好ましくは５，０００ｇ／ｅｑ以上であることを意味する。この範囲内であれば、優れた保存安定性が得られる。 <Photosensitive curable composition>
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.
In the present invention, 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.
［（Ａ）カルボジイミド基を有する化合物］
　本発明の感光性硬化性組成物は、（Ａ）カルボジイミド基を有する化合物を含む。このカルボジイミド基を有する化合物は、分子構造中にカルボジイミド基（－Ｎ＝Ｃ＝Ｎ－）を含む化合物であり、公知の方法にて合成することができる（例えば、特開２０１９－３８９６０号公報参照）。具体的には、ジイソシアネートを縮合重合して合成することができる。 [(A) Compound having a carbodiimide group]
The photosensitive curable composition of the present invention contains (A) a compound having a carbodiimide group. This compound having a carbodiimide group is a compound containing a carbodiimide group (-N = C = N-) in its molecular structure, and can be synthesized by a known method (see, for example, JP-A-2019-38960). ). Specifically, it can be synthesized by condensation polymerization of diisocyanate.
　このような分子構造中に含まれるカルボジイミド基は、常温（約２５℃）以上でカルボキシル基と架橋反応してＮ－アシルウレア結合を形成し、常温（約２５℃）以上でフェノール性水酸基と架橋反応してウレア結合を形成し、１５０℃以上でアミノ基と架橋反応してグアニジン結合を形成し、１５０℃以上でエポキシ基と架橋反応してイミダゾリジオン環結合を形成し、そして、１８０℃以上でカルボジイミド基が自己架橋反応してトリアジン環結合を形成する。なかでも、イミダゾリジオン環結合とトリアジン環結合を形成した硬化物は、優れた誘電特性（低誘電率や低誘電正接）を示し、かつ優れた耐熱性（高いガラス転移温度）を示す。
　この点で、本発明においては、組成物中にカルボキシル基および／またはフェノール性水酸基を有する化合物を実質的に含まない場合には、この化合物（Ａ）中のカルボジイミド基とカルボキシル基やフェノール性水酸基との反応に起因した架橋反応が常温にて生起し難くなり、優れた保存安定性を示す。 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. To form a urea bond, 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. Among them, 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).
In this respect, in the present invention, when 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.
　このような（Ａ）カルボジイミド基を有する化合物の合成に用いるジイソシアネートとしては、芳香族ジイソシアネート、脂肪族ジイソシアネート、脂環族ジイソシアネートがある。具体的には、１，５－ナフチレンジイソシアネート、２，４’－ジフェニルメタンジイソシアネート、４，４’－ジフェニルメタンジイソシアネート、４，４’－ジフェニルジメチルメタンジイソシアネート、１，３－フェニレンジイソシアネート、１，４－フェニレンジイソシアネート、２，４－トリレンジイソシアネート、２，６－トリレンジイソシアネート、ｏ－キシリレンジイソシアネート、ｍ－キシリレンジイソシアネート、テトラメチルキシリレンジイソシアネート等の芳香族ジイソシアネート、メチレンジイソシアネート、テトラメチレンジイソシアネート、ヘキサメチレンジイソシアネート、トリメチルヘキサメチレンジイソシアネート等の脂肪族ジイソシアネート、シクロヘキサン－１，４－ジイソシアネート、イソホロンジイソシアネート、ジシクロヘキシルメタン－４，４’－ジイソシアネート、メチルシクロヘキサンジイソシアネート、２，５－ビス（イソシアナトメチル）ビシクロ［２．２．１］ヘプタン、２，６－ビス（イソシアナトメチル）ビシクロ［２．２．１］ヘプタン等の脂環族ジイソシアネート等が挙げられる。
　これらのジイソシアネートは、１種単独でも、２種以上併用してもよく、反応性や硬化物としての耐熱性の観点から芳香族ジイソシアネート、有機溶剤への溶解性や硬化物としての柔軟性や低誘電特性の観点から脂肪族ジイソシアネートや脂環族ジイソシアネートを適宜用いることができる。
　特に、本発明において用いられる（Ａ）カルボジイミド基を有する化合物としては、有機溶剤への溶解性、保存安定性、反応性、硬化物の耐熱性といった特性をバランスよく実現することから、２，４’－ジフェニルメタンジイソシアネートと４，４’－ジフェニルメタンジイソシアネートを併用して縮合重合させてなる化合物が好ましい。 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, hexa. 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.
These 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.
In particular, 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.
　このようにして得られる（Ａ）カルボジイミド基を有する化合物は、末端イソシアネート基を有するが、この末端イソシアネート基は、組成物中にアルコール性水酸基が存在した場合に保存安定性が悪化するという観点から、イソシアネート基と反応する官能基を１つ有する化合物で封止反応することが好ましい。このイソシアネート基と反応する化合物としては、モノイソシアネート、モノアルコール、モノアミン、酸無水物等が挙げられる。 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. , It is preferable to carry out a sealing reaction with a compound having one functional group that reacts with an isocyanate group. Examples of the compound that reacts with this isocyanate group include monoisocyanate, monoalcohol, monoamine, and acid anhydride.
　モノイソシアネートとしては、例えば、メチルイソシアネート、エチルイソシアネート、プロピルイソシアネート、ｎ－、ｓｅｃ－或いはｔｅｒｔ－ブチルイソシアネート等の低級アルキルイソシアネート、シクロヘキシルイソシアネート等の脂環式脂肪族イソシアネート、フェニルイソシアネート、トリルイソシアネート、ジメチルフェニルイソシアネート、２，６－ジイソプロピルフェニルイソシアネート等の芳香族イソシアネート等が挙げられる。
　モノアルコールとしては、例えば、メタノール、エタノール、シクロヘキサノール、ポリエチレングリコールモノメチルエーテル、ポリプロピレングリコールモノメチルエーテル等が挙げられる。
　前記モノアミンとしては、例えば、ブチルアミン、シクロヘキシルアミン等の１級アミン、ジエチルアミン、ジブチルアミン、ジシクロヘキシルアミン等の２級アミンが挙げられる。
　酸無水物としては、無水フタル酸、無水酢酸、無水コハク酸、無水マレイン酸、無水安息香酸等が挙げられる。
　これらは、単独で用いてもよく、２種以上を組み合わせて用いてもよい。なかでも、反応性の観点から、フェニルイソシアネート、トリルイソシアネートが好ましく、フェニルイソシアネートがより好ましい。 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.
　このような（Ａ）カルボジイミド基を有する化合物は、１種を単独または２種以上を組み合わせて用いることができる。
　また、このカルボジイミド基を有する化合物は、後述する有機コバルト錯体や有機マンガン錯体等の有機金属錯体又は有機金属塩等の硬化促進剤を配合することで、自己架橋反応（トリアジン環結合の形成）を促進し、低温硬化性を付与することができる。 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.
　本発明の感光性硬化性組成物を構成する（Ａ）カルボジイミド基を有する化合物は、カルボジイミド基を有する化合物としての有機溶剤への溶解性や保存安定性、感光性硬化性組成物としての露光部の現像液耐性や未露光部の現像液溶解性の観点から、その重量平均分子量（Ｍｗ）が１，０００～１０，０００であることが好ましく、１，５００～５，０００であることがより好ましい。本明細書において、重量平均分子量はゲルパーミエーションクロマトグラフィー（ＧＰＣ）により測定し、標準ポリスチレンで換算した値である。
　また、この（Ａ）カルボジイミド基を有する化合物は、反応性の観点から、カルボジイミド基当量（ｇ／ｅｑ）が１００～５００であることが好ましく、１５０～３５０であることがより好ましい。
　また、この（Ａ）カルボジイミド基を有する化合物は、有機溶剤を除く組成物の全有機成分中に５０～９９質量％の割合で配合されていることが好ましい。この範囲で配合することにより、優れた誘電特性と耐熱性を有する硬化物を得ることができる。 (A) 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. From the viewpoint of developer resistance and developer solubility of unexposed areas, the weight average molecular weight (Mw) is preferably 1,000 to 10,000, and more preferably 1,500 to 5,000. preferable. In the present specification, the weight average molecular weight is a value measured by gel permeation chromatography (GPC) and converted into standard polystyrene.
Further, 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.
［（Ｂ）光によってカルボキシル基および／またはフェノール性水酸基を生成する化合物］
　本発明の感光性硬化性組成物は、（Ｂ）光によってカルボキシル基および／またはフェノール性水酸基を生成する化合物、好ましくはナフトキノンジアジド化合物を含む。
　この化合物（Ｂ）は、光照射（露光）によって、カルボキシル基および／またはフェノール性水酸基を生成する化合物であり、未露光の状態では、化合物（Ａ）中のカルボジイミド基と架橋反応を生じる官能基を生成しないものである。
　その結果、本発明の感光性硬化性組成物からなる乾燥塗膜をパターン露光した場合、露光部の化合物（Ｂ）より生成されたカルボキシル基および／またはフェノール性水酸基と（Ａ）カルボジイミド基を有する化合物のカルボジイミド基とが、常温（約２５℃）以上で架橋反応することで、露光部は現像液に溶解しなくなり、未露光部との現像性の差から、塗膜のパターンが形成される。 [(B) A compound that produces a carboxyl group and / or a phenolic hydroxyl group by light]
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.
As a result, when the dry coating film made of the photosensitive curable composition of the present invention is 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. When 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. ..
　このような光によってカルボキシル基および／またはフェノール性水酸基を生成する化合物としては、公知慣用の化合物を用いることができるが、特に光によってカルボキシル基を生成するナフトキノンジアジド化合物が好ましい。このナフトキノンジアジド化合物としては、例えば、テトラヒドロキシベンゾフェノンのナフトキノンジアジド付加物（例えば、三宝化学研究所社製のＢＳ５７０（付加率７０％），ＢＳ５９９（付加率９９％））や、４－｛４－［１，１－ビス（４－ヒドロキシフェニル）エチル］－α，α－ジメチルベンジル｝フェノールのナフトキノンジアジド付加物（例えば、三宝化学研究所社製のＴＫＦ－４２８（付加率９３％），ＴＫＦ－５２８（付加率９３％））等が挙げられる。これらは、単独で用いてもよく、２種以上を組み合わせて用いてもよい。なかでも、有機溶剤への溶解性の観点から、４－｛４－［１，１－ビス（４－ヒドロキシフェニル）エチル］－α，α－ジメチルベンジル｝フェノールのナフトキノンジアジド付加物が好ましい。 As a compound that generates a carboxyl group and / or a phenolic hydroxyl group by such light, a known and commonly used compound can be used, but a naphthoquinone diazide compound that generates a carboxyl group by light is particularly preferable. Examples of 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-. [1,1-Bis (4-hydroxyphenyl) ethyl] -α, α-dimethylbenzyl} 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] -α, α-dimethylbenzyl} phenol is preferable from the viewpoint of solubility in an organic solvent.
　上記のナフトキノンジアジド化合物は、ナフトキノンジアジドの付加率に応じて、フェノール性水酸基が残存することから、保存安定性が低下する可能性がある。そのため、組成物中にフェノール性水酸基を有する化合物を実質的に含まないように、ナフトキノンジアジドの付加率は、６０％以上が好ましく、７５％以上がより好ましく、８０％以上であることが最も好ましい。 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. ..
　（Ｂ）光によってカルボキシル基および／またはフェノール性水酸基を生成する化合物は、組成物中の（Ａ）カルボジイミド基を有する化合物との関係で、化合物（Ａ）のカルボジイミド基と、化合物（Ｂ）が露光によって生成するカルボキシル基および／またはフェノール性水酸基との当量比（カルボジイミド基：カルボキシル基および／またはフェノール性水酸基）が、１：０．０１～０．２となるように配合することが好ましく、１：０．０２～０．１であることがより好ましく、１：０．０３～０．０８であることが最も好ましい。このような当量比の関係にあれば、露光部の現像液耐性が得られ、かつ、カルボジイミド基がトリアジン環やイミダゾリジオン環といった架橋構造を多く形成し、優れた誘電特性と耐熱性が得られる。 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. With such an equivalent ratio relationship, 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.
［２５℃において液状である有機化合物］
　本発明の感光性硬化性組成物は、化合物（Ａ）と化合物（Ｂ）以外に、優れた誘電特性と耐熱性を損なわない範囲内で、２５℃において液状である有機化合物を配合することができる。 [Organic compounds that are liquid at 25 ° C]
In addition to the compound (A) and the compound (B), 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.
　この２５℃において液状である有機化合物は、組成物の軟化点を下げる効果を有し、未露光部の現像液溶解性を向上させると共に、後述するドライフィルムの組成物層の割れや裁断時の粉落ちを抑制し、ラミネート時の組成物流動性を向上させる機能を有し、配合量は、有機溶剤を除く組成物の有機成分中、１０～４０質量％であることが好ましい。 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.
　このような機能を有する２５℃において液状である有機化合物としては、カルボキシル基および／またはフェノール性水酸基を実質的に有していなければ、特に限定されるものではない。なかでも、環状（チオ）エーテル基および／またはエチレン性不飽和結合を有する有機化合物を用いることが好ましい。 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.
（環状（チオ）エーテル基を有する有機化合物）
　２５℃において液状である環状（チオ）エーテル基を有する有機化合物としては、具体的には、エポキシ基、エピスルフィド基、オキセタン基を有する化合物が挙げられる。このような環状（チオ）エーテル基は、カルボジイミド基と１５０℃以上で架橋反応し、イミダゾリジオン環やイミダゾリジンチオン環結合を形成する。イミダゾリジオン環やイミダゾリジンチオン環結合を形成した硬化物は、より一層の優れた誘電特性（低誘電率や低誘電正接）を有し、優れた耐熱性（高いガラス転移温度）を有するものとなる。 (Organic compound having a cyclic (thio) ether group)
Specific examples of the organic compound having a cyclic (thio) ether group that is liquid at 25 ° C. include a compound having an epoxy group, an episulfide group, and an oxetane group. 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). ..
　２５℃において液状であるエポキシ基を有する有機化合物としては、公知慣用のものを用いることができ、例えば、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＳ型エポキシ樹脂、ビスフェノールＡＦ型エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂、トリスフェノール型エポキシ樹脂、ナフトールノボラック型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、エステル骨格を有する脂環式エポキシ樹脂、ｔｅｒｔ－ブチル－カテコール型エポキシ樹脂、ナフタレン型エポキシ樹脂、ナフトール型エポキシ樹脂、アントラセン型エポキシ樹脂、グリシジルアミン型エポキシ樹脂、グリシジルエステル型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、ビフェニル型エポキシ樹脂、線状脂肪族エポキシ樹脂、ブタジエン構造を有するエポキシ樹脂、脂環式エポキシ樹脂、複素環式エポキシ樹脂、スピロ環含有エポキシ樹脂、シクロヘキサンジメタノール型エポキシ樹脂、ナフチレンエーテル型エポキシ樹脂、トリメチロール型エポキシ樹脂、テトラフェニルエタン型エポキシ樹脂等が挙げられる。 As the organic compound having an epoxy group that is liquid at 25 ° C., known and commonly used ones can be used. For example, 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.
　２５℃において液状であるエピスルフィド基を有する有機化合物としては、上記液状のエポキシ基を有する有機化合物のエポキシ基（オキシラン環）にチオ尿素等の硫化剤を反応させて、エピスルフィド基（チイラン環）に置換した有機化合物が挙げられる。 As the organic compound having an episulfide group that is liquid at 25 ° C., 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). Substituted organic compounds can be mentioned.
　２５℃において液状であるオキセタン基を有する有機化合物としては、３－エチル－３－ヒドロキシメチルオキセタン、３－エチル－３－（フェノキシメチル）オキセタン、３－エチル－３－（２－エチルヘキシロキシメチル）オキセタン、１，４－ビス｛［（３－エチル－３－オキセタニル）メトキシ］メチル｝ベンゼン、ビス（３－エチル－３－オキセタニルメチル）エーテルなどが挙げられる。 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.
　このような２５℃において液状である環状（チオ）エーテル基を有する有機化合物は、１種を単独または２種以上を組み合わせて用いることができる。
　この環状（チオ）エーテル基を有する有機化合物は、後述するイミダゾール等の硬化促進剤を配合することで、低温硬化性を付与することができる。
　また、環状（チオ）エーテル基を有する有機化合物の分子構造に由来する公知慣用の効果は、本発明においても有効である。具体的には、エピスルフィド基に由来する密着性付与、低温硬化性付与、オキセタン基による保存安定性付与、ジシクロペンタジエン骨格による低誘電特性付与、ビスフェノールＳ型構造、トリスフェノール型構造、ナフタレン型構造、アントラセン型構造、ビフェニル型構造による難燃性付与、ナフタレン型構造、ビフェニル型構造による低熱膨張性付与、熱伝導性付与、線状脂肪族構造や脂環式構造による溶剤溶解性、柔軟性、保存安定性といった特性付与等が挙げられる。 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. Specifically, adhesion imparted by episulfide group, low temperature curability imparted, storage stability imparted by oxetane group, low dielectric property imparted by dicyclopentadiene skeleton, bisphenol S type structure, trisphenol type structure, naphthalene type structure , Anthracene type structure, flame retardancy imparted by biphenyl type structure, naphthalene type structure, low thermal expansion imparted by biphenyl type structure, thermal conductivity imparted, solvent solubility by linear aliphatic structure or alicyclic structure, flexibility, Examples include imparting characteristics such as storage stability.
（エチレン性不飽和結合を有する有機化合物）
　２５℃において液状であるエチレン性不飽和結合を有する有機化合物としては、具体的には、ポリエステル（メタ）アクリレート、ポリエーテル（メタ）アクリレート、ウレタン（メタ）アクリレート、カーボネート（メタ）アクリレート、エポキシ（メタ）アクリレートなどが挙げられる。
　本発明の感光性硬化性組成物では、このようなエチレン性不飽和結合を有する有機化合物と後述する光重合開始剤とを併用することで、光照射（露光）によるラジカル重合性を付与することができる。このような構成によれば、組成物の乾燥塗膜において、露光部では、上述の化合物（Ａ）と化合物（Ｂ）の架橋反応に加えて、エチレン性不飽和結合を有する有機化合物のラジカル重合反応が生起し、露光部の現像液耐性がさらに向上する。 (Organic compound with ethylenically unsaturated bond)
Specific examples of the 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.
In the photosensitive curable composition of the present invention, 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. According to such a configuration, in the dry coating film of the composition, in the exposed portion, in addition to the above-mentioned cross-linking reaction between the compound (A) and the compound (B), radical polymerization of an organic compound having an ethylenically unsaturated bond A reaction occurs, and the developer resistance of the exposed portion is further improved.
　２５℃において液状であるエチレン性不飽和結合を有する有機化合物としては、公知慣用のものを用いることができ、例えば、２－ヒドロキシエチルアクリレート、２－ヒドロキシプロピルアクリレートなどのヒドロキシアルキルアクリレート類、エチレングリコール、メトキシテトラエチレングリコール、ポリエチレングリコール、プロピレングリコールなどのグリコールのジアクリレート類、Ｎ，Ｎ－ジメチルアクリルアミド、Ｎ－メチロールアクリルアミド、Ｎ，Ｎ－ジメチルアミノプロピルアクリルアミドなどのアクリルアミド類、Ｎ，Ｎ－ジメチルアミノエチルアクリレート、Ｎ，Ｎ－ジメチルアミノプロピルアクリレートなどのアミノアルキルアクリレート類、ヘキサンジオール、トリメチロールプロパン、ペンタエリスリトール、ジペンタエリスリトール、トリス－ヒドロキシエチルイソシアヌレートなどの多価アルコールまたはこれらのエチレンオキサイド付加物、プロピレンオキサイド付加物、もしくはε－カプロラクトン付加物などの多価アクリレート類、ビスフェノールＡのエチレンオキサイド付加物もしくはプロピレンオキサイド付加物等の多価アクリレート類、グリセリンジグリシジルエーテル、グリセリントリグリシジルエーテル、トリメチロールプロパントリグリシジルエーテル、トリグリシジルイソシアヌレートなどのグリシジルエーテルの多価アクリレート類、前記に限らず、ポリエーテルポリオール、ポリカーボネートジオール、水酸基末端ポリブタジエン、ポリエステルポリオールなどのポリオールを直接アクリレート化、もしくは、ジイソシアネートを介してウレタンアクリレート化したアクリレート類及びメラミンアクリレート、及び前記アクリレートに対応する各メタクリレート類が挙げられる。
　なかでも柔軟性と反応性に優れることから、トリメチロールプロパン、ビスフェノールＡのエチレンオキサイド付加物および／またはプロピレンオキサイド付加物が好ましい。 As the 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. , Polyvalent acrylates such as propylene oxide adducts or ε-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.
Of these, trimethylolpropane, an ethylene oxide adduct of bisphenol A and / or a propylene oxide adduct are preferable because of their excellent flexibility and reactivity.
　このような２５℃において液状であるエチレン性不飽和結合を有する有機化合物は、１種を単独または２種以上を組み合わせて用いることができる。 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.
　ここで、「２５℃において液状」であるかの確認は、危険物の試験及び性状に関する省令（平成元年自治省令第１号）の別紙第２の「液状の確認方法」に準じて行う。具体的な、評価方法を以下に記載する。 Here, confirmation of whether or not it is "liquid at 25 ° C" is performed in accordance with the attached second "Confirmation method of liquid" of the Ministerial Ordinance on Dangerous Goods Test and Properties (Ministry of Home Affairs Ordinance No. 1 of 1989). The specific evaluation method is described below.
（１）装置
　恒温水槽：攪拌機、ヒーター、温度計、自動温度調節器（±０．１℃で温度制御が可能なもの）を備えたもので深さ１５０ｍｍ以上のものを用いる。例えば、ヤマト科学社製の低温恒温水槽（型式ＢＵ３００）と投入式恒温装置サーモメイト（型式ＢＦ５００）の組み合わせ、水道水約２２リットルを低温恒温水槽に入れ、これに組み付けられたサーモメイトの電源を入れて２５℃に設定し、水温を設定温度±０．１℃に調整する。
　試験管：試験管としては、図１に示すように、内径３０ｍｍ、高さ１２０ｍｍの平底円筒型透明ガラス製のもので、管底から５５ｍｍおよび８５ｍｍの高さのところにそれぞれ標線１１、１２が付され、試験管の口をゴム栓１３ａで密閉した液状判定用試験管１０ａと、同じサイズで同様に標線が付され、中央に温度計を挿入・支持するための孔があけられたゴム栓１３ｂで試験管の口を密閉し、ゴム栓１３ｂに温度計１４を挿入した温度測定用試験管１０ｂを用いる。以下、管底から５５ｍｍの高さの標線１１を「Ａ線」、管底から８５ｍｍの高さの標線１２を「Ｂ線」という。
　温度計１４としては、ＪＩＳ　Ｂ７４１０（１９８２）「石油類試験用ガラス製温度計」に規定する凝固点測定用のもの（ＳＯＰ－５８目盛範囲２０～５０℃）を用いるが、０～５０℃の温度範囲が測定できるものであればよい。 (1) 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. For example, a combination of a low temperature constant temperature water tank (model BU300) manufactured by Yamato Kagaku Co., Ltd. and a charging type constant temperature device Thermomate (model BF500), about 22 liters of tap water is put into the low temperature constant temperature water tank, and the power supply of the thermomate attached to this is put into it. Put it in and set it to 25 ° C, and adjust the water temperature to the set temperature ± 0.1 ° C.
Test tube: As shown in FIG. 1, 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. Hereinafter, the marked line 11 having a height of 55 mm from the bottom of the pipe is referred to as "line A", and the marked line 12 having a height of 85 mm from the bottom of the pipe is referred to as "line B".
As 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.
（２）実施手順
　温度２０±５℃の大気圧下で２４時間以上放置した試料を、図１（ａ）に示す液状判定用試験管１０ａと図１（ｂ）に示す温度測定用試験管１０ｂにそれぞれＡ線まで入れる。２本の試験管１０ａ、１０ｂを低温恒温水槽にＢ線が水面下になるように直立させて静置する。温度計は、その下端がＡ線よりも３０ｍｍ下となるようにする。
　試料温度が設定温度±０．１℃に達してから１０分間そのままの状態を保持する。１０分後、液状判断用試験管１０ａを低温恒温水槽から取り出し、直ちに水平な試験台の上に水平に倒し、試験管内の液面の先端がＡ線からＢ線まで移動した時間をストップウォッチで測定し、記録する。試料は、設定温度において、測定された時聞が９０秒以内のものを液状、９０秒を超えるものを固体状と判定する。 (2) Implementation procedure Samples left for 24 hours or more under atmospheric pressure at a temperature of 20 ± 5 ° C. are subjected to the liquid determination test tube 10a shown in FIG. 1 (a) and the temperature measurement test tube 10b shown in FIG. 1 (b). Put up to line A in each. The two test tubes 10a and 10b are placed upright in a low-temperature constant temperature water tank so that the line B is below the water surface. The thermometer should have its lower end 30 mm below line A.
After the sample temperature reaches the set temperature ± 0.1 ° C, keep it as it is for 10 minutes. 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.
［硬化促進剤］
　本発明の感光性硬化性組成物は、さらに硬化促進剤を含有することができる。
　硬化促進剤としては、例えば、１，８－ジアザビシクロ［５．４．０］ウンデセン－７、１，５－ジアザビシクロ［４．３．０］ノネン－５、５，６－ジブチルアミノ－１，８－ジアザビシクロ［５．４．０］ウンデセン－７等のシクロアミジン化合物、ジシアンジアミド、ベンジルジメチルアミン、４－（ジメチルアミノ）－Ｎ，Ｎ－ジメチルベンジルアミン、４－メトキシ－Ｎ，Ｎ－ジメチルベンジルアミン、４－メチル－Ｎ，Ｎ－ジメチルベンジルアミン等のアミン化合物、イミダゾール、２－メチルイミダゾール、２－エチルイミダゾール、２－エチル－４－メチルイミダゾール、２－フェニルイミダゾール、４－フェニルイミダゾール、１－シアノエチル－２－フェニルイミダゾール、１－（２－シアノエチル）－２－エチル－４－メチルイミダゾール、１－ベンジル－２－フェニルイミダゾール等のイミダゾール化合物及びその誘導体、トリブチルホスフィン、メチルジフェニルホスフィン、トリフェニルホスフィン、トリス（４－メチルフェニル）ホスフィン、ジフェニルホスフィン、フェニルホスフィン等の有機ホスフィン化合物、コバルト（ＩＩ）アセチルアセトナート、コバルト（ＩＩＩ）アセチルアセトナート等の有機コバルト錯体、銅（ＩＩ）アセチルアセトナート等の有機銅錯体、亜鉛（ＩＩ）アセチルアセトナート等の有機亜鉛錯体、鉄（ＩＩＩ）アセチルアセトナート等の有機鉄錯体、ニッケル（ＩＩ）アセチルアセトナート等の有機ニッケル錯体、マンガン（ＩＩ）アセチルアセトナート等の有機マンガン錯体等の有機金属錯体又は有機金属塩が挙げられる。
　これらは１種を単独で用いても２種以上組み合わせて用いてもよい。
　このような硬化促進剤は、上述の（Ａ）カルボジイミド基を有する化合物や環状（チオ）エーテル基を有する化合物と併用する場合には、その配合量を、（Ａ）カルボジイミド基を有する化合物の量、または（Ａ）カルボジイミド基を有する化合物と環状（チオ）エーテル基を有する化合物の合計量に対して０．０１～１０質量％とすることが好ましい。 [Curing accelerator]
The photosensitive curable composition of the present invention can further contain a curing accelerator.
Examples of 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. -Diazabicyclo [5.4.0] 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 Examples thereof include 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.
When such a curing accelerator is used in combination with the above-mentioned compound having a carbodiimide group or a compound having a cyclic (thio) ether group, the blending amount thereof is adjusted to the amount of the compound having a carbodiimide group (A). , Or (A) 0.01 to 10% by mass based on the total amount of the compound having a carbodiimide group and the compound having a cyclic (thio) ether group.
［光重合開始剤］
　本発明の感光性硬化性組成物は、さらに光重合開始剤を含有することができる。
　光重合開始剤としては、例えば、ビス－（２，６－ジクロロベンゾイル）フェニルフォスフィンオキサイド、ビス－（２，６－ジクロロベンゾイル）－２，５－ジメチルフェニルフォスフィンオキサイド、ビス－（２，６－ジクロロベンゾイル）－４－プロピルフェニルフォスフィンオキサイド、ビス－（２，６－ジクロロベンゾイル）－１－ナフチルフォスフィンオキサイド、ビス－（２，６－ジメトキシベンゾイル）フェニルフォスフィンオキサイド、ビス－（２，６－ジメトキシベンゾイル）－２，４，４－トリメチルペンチルフォスフィンオキサイド、ビス－（２，６－ジメトキシベンゾイル）－２，５－ジメチルフェニルフォスフィンオキサイド、ビス－（２，４，６－トリメチルベンゾイル）－フェニルフォスフィンオキサイド等のビスアシルフォスフィンオキサイド類、２，６－ジメトキシベンゾイルジフェニルフォスフィンオキサイド、２，６－ジクロロベンゾイルジフェニルフォスフィンオキサイド、２，４，６－トリメチルベンゾイルフェニルフォスフィン酸メチルエステル、２－メチルベンゾイルジフェニルフォスフィンオキサイド、ピバロイルフェニルフォスフィン酸イソプロピルエステル、２，４，６－トリメチルベンゾイルジフェニルフォスフィンオキサイド等のモノアシルフォスフィンオキサイド類、フェニル（２，４，６－トリメチルベンゾイル）ホスフィン酸エチル、１－ヒドロキシ－シクロヘキシルフェニルケトン、１－［４－（２－ヒドロキシエトキシ）－フェニル］－２－ヒドロキシ－２－メチル－１－プロパン－１－オン、２－ヒドロキシ－１－｛４－［４－（２－ヒドロキシ－２－メチル－プロピオニル）－ベンジル］フェニル｝－２－メチル－プロパン－１－オン、２－ヒドロキシ－２－メチル－１－フェニルプロパン－１－オン等のヒドロキシアセトフェノン類、ベンゾイン、ベンジル、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインｎ－プロピルエーテル、ベンゾインイソプロピルエーテル、ベンゾインｎ－ブチルエーテル等のベンゾイン類、ベンゾインアルキルエーテル類、ベンゾフェノン、ｐ－メチルベンゾフェノン、ミヒラーズケトン、メチルベンゾフェノン、４，４’－ジクロロベンゾフェノン、４，４’－ビスジエチルアミノベンゾフェノン等のベンゾフェノン類、アセトフェノン、２，２－ジメトキシ－２－フェニルアセトフェノン、２，２－ジエトキシ－２－フェニルアセトフェノン、１，１－ジクロロアセトフェノン、１－ヒドロキシシクロヘキシルフェニルケトン、２－メチル－１－［４－（メチルチオ）フェニル］－２－モルフォリノ－１－プロパノン、２－ベンジル－２－ジメチルアミノ－１－（４－モルフォリノフェニル）－ブタノン－１、２－（ジメチルアミノ）－２－［（４－メチルフェニル）メチル］－１－［４－（４－モルホリニル）フェニル］－１－ブタノン、Ｎ，Ｎ－ジメチルアミノアセトフェノン等のアセトフェノン類、チオキサントン、２－エチルチオキサントン、２－イソプロピルチオキサントン、２，４－ジメチルチオキサントン、２，４－ジエチルチオキサントン、２－クロロチオキサントン、２，４－ジイソプロピルチオキサントン等のチオキサントン類、アントラキノン、クロロアントラキノン、２－メチルアントラキノン、２－エチルアントラキノン、２－ｔｅｒｔ－ブチルアントラキノン、１－クロロアントラキノン、２－アミルアントラキノン、２－アミノアントラキノン等のアントラキノン類、アセトフェノンジメチルケタール、ベンジルジメチルケタール等のケタール類、エチル－４－ジメチルアミノベンゾエート、２－（ジメチルアミノ）エチルベンゾエート、ｐ－ジメチル安息香酸エチルエステル等の安息香酸エステル類、１，２－オクタンジオン，１－［４－（フェニルチオ）－，２－（Ｏ－ベンゾイルオキシム）］、エタノン，１－［９－エチル－６－（２－メチルベンゾイル）－９Ｈ－カルバゾール－３－イル］－，１－（Ｏ－アセチルオキシム）等のオキシムエステル類、ビス（η５－２，４－シクロペンタジエン－１－イル）－ビス（２，６－ジフルオロ－３－（１Ｈ－ピロール－１－イル）フェニル）チタニウム、ビス（シクロペンタジエニル）－ビス［２，６－ジフルオロ－３－（２－（１－ピル－１－イル）エチル）フェニル］チタニウム等のチタノセン類、フェニルジスルフィド２－ニトロフルオレン、ブチロイン、アニソインエチルエーテル、アゾビスイソブチロニトリル、テトラメチルチウラムジスルフィド等を挙げることができる。
　これらは、単独で用いてもよく、２種以上を組み合わせて用いてもよい。
　このような光重合開始剤は、上述のエチレン性不飽和結合を有する有機化合物と併用して用いる場合には、その配合量を、エチレン性不飽和結合を有する有機化合物に対して０．１～１０質量％とすることが好ましい。 [Photopolymerization initiator]
The photosensitive curable composition of the present invention can further contain a photopolymerization initiator.
Examples of 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-dimethylphenylphosphine oxide, bis- (2,4,6- Bisacylphosphine oxides such as trimethylbenzoyl) -phenylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylphenylphosphine Monoacylphosphine oxides such as acid methyl ester, 2-methylbenzoyldiphenylphosphine oxide, pivaloylphenylphosphinic acid isopropyl ester, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, phenyl (2,4) 6-trimethylbenzoyl) ethyl phosphinate, 1-hydroxy-cyclohexylphenylketone, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1-one, 2- Hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propane-1-one, 2-hydroxy-2-methyl-1-phenylpropane- Hydroxyacetophenones such as 1-one, benzoin, benzyl, benzoin methyl ether, benzoin ethyl ether, benzoin n-propyl ether, benzoin isopropyl ether, benzoin such as benzoin n-butyl ether, benzoyl alkyl ethers, benzophenone, p-methyl Benzoyls such as benzophenone, Michler's ketone, methylbenzophenone, 4,4'-dichlorobenzophenone, 4,4'-bisdiethylaminobenzophenone, acetophenone, 2,2-dimethoxy-2-phenylacetophenone , 2,2-Diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexylphenylketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2 -Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) ) Phenyl] -1-butanone, acetophenones such as N, N-dimethylaminoacetophenone, thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone , 2,4-Diisopropylthioxanthone and other thioxanthones, anthraquinone, chloroanthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylantraquinone, 1-chloroanthraquinone, 2-amylanthraquinone, 2-aminoanthraquinone and the like. 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 (η5-2,4-cyclopentadiene-1-yl) -bis (2,6-difluoro-3- (1H-pyrrole-1-yl)) Oxime) Titanium, bis (cyclopentadienyl) -bis [2,6-difluoro-3- (2- (1-pyr-1-yl) ethyl) phenyl] Titanocenes such as titanium, phenyldisulfide 2-nitrofluorene , Butyloin, anisoin ethyl ether, azobisisobutyronitrile, tetramethylthium disulfide and the like.
These may be used alone or in combination of two or more.
When such a photopolymerization initiator is used in combination with the above-mentioned organic compound having an ethylenically unsaturated bond, 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.
［有機溶剤］
　本発明の感光性硬化性組成物は、さらに有機溶剤を含有することができる。
　有機溶剤は、組成物の主成分である（Ａ）カルボジイミド基を有する化合物に対して溶解性に優れるもの（良溶媒）を選択することが好ましい。このような良溶媒である有機溶剤としては、例えば、テトラヒドロフラン、１，３－ジオキサン、ジオキソラン等の脂環式エーテル、ベンゼン、トルエン、キシレン、エチルベンゼン等の芳香族炭化水素、クロロベンゼン、ジクロロベンゼン、トリクロロベンゼン、パークレン、トリクロロエタン、ジクロロエタン等のハロゲン化炭化水素、シクロヘキサノン、石油ナフサ等が挙げられる。なかでも、低価格や低毒性の観点から、シクロヘキサノンと石油ナフサが好ましい。石油ナフサは、沸点範囲が８０～１８０℃の重質ナフサが好ましく、市販品としては、三協化学製のソルベント＃１００、ソルベント＃１５０、ソルベントナフサ、出光昭和シェル製のイプゾール＃１００、イプゾール＃１５０、イプゾールＴＰ、ＪＸＴＧエネルギー製のＴ－ＳＯＬ１００、Ｔ－ＳＯＬ１５０、カクタスソルベントＰ－１００、カクタスソルベントＰ－１５０、カクタスソルベントＰ－１８０、カクタスファインＳＦ－０１、カクタスファインＳＦ－０２、安藤パラケミー製のＮＤソルベント１５０が挙げられる。 [Organic solvent]
The photosensitive curable composition of the present invention can further contain an organic solvent.
As the 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. As 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. 150, Ipsol TP, T-SOL100, T-SOL150 made by JXTG Energy, Cactus Solvent P-100, Cactus Solvent P-150, Cactus Solvent P-180, Cactus Fine SF-01, Cactus Fine SF-02, Made by Ando Parachemy ND Solvent 150 can be mentioned.
　これらは、単独でもよく、２種以上を組み合わせて用いてもよい。また、このような有機溶剤との併用であれば、（Ａ）カルボジイミド基を有する化合物に対して貧溶媒である有機溶剤も併用して配合することが可能である。
　そして、有機溶剤の含有量は特に限定されず、硬化性組成物の用途に応じて適宜調整可能である。 These may be used alone or in combination of two or more. Further, when used in combination with such an organic solvent, it is possible to combine (A) a compound having a carbodiimide group with an organic solvent which is a poor solvent.
The content of the organic solvent is not particularly limited, and can be appropriately adjusted according to the use of the curable composition.
［無機充填材］
　本発明の感光性硬化性組成物は、さらに無機充填材を含有することができる。
　無機充填材としては公知慣用のものを用いることができ、例えば、硫酸バリウム、チタン酸バリウム、無定形シリカ、結晶性シリカ、溶融シリカ、球状シリカ、タルク、クレー、炭酸マグネシウム、炭酸カルシウム、酸化アルミニウム、水酸化アルミニウム、水酸化マグネシウム、窒化ケイ素、窒化ホウ素、窒化アルミニウム、銀粉末、銅粉粉末、はんだ粉末等が挙げられる。
　これらは、単独でもよく、２種以上を組み合わせて用いてもよい。 [Inorganic filler]
The photosensitive curable composition of the present invention can further contain an inorganic filler.
Known and commonly used 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. , Aluminum hydroxide, magnesium hydroxide, silicon nitride, boron nitride, aluminum nitride, silver powder, copper powder, solder powder and the like.
These may be used alone or in combination of two or more.
　これらの無機充填材の形状は、充填性や組成物の流動性、ドライフィルムとしてのハンドリングが向上することから、球状が好ましく、より高充填化する場合は、主たる球状の無機充填材と、主たる無機充填材の平均粒子径に対して１／５～１／５０の平均粒子径を有する球状の無機充填材を組み合せることがより好ましい。
　また、無機充填材の平均粒子径は、５０ｎｍ～２０μｍの範囲で適宜選択することができ、露光時の光透過性、ひいてはパターン解像性が向上することから、平均粒子径は５０ｎｍ～２μｍであることが好ましく、充填性や組成物の流動性が向上することから、平均粒子径は１μｍ～２０μｍであることが好ましい。
　なお、本発明における平均粒子径とは、レーザー回折法により測定されたＤ５０の値である。レーザー回折法による測定装置としては、日機装社製のＭｉｃｒｏｔｒａｃ　ＭＴ３３００ＥＸＩＩが挙げられる。 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. In the case of higher filling, 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.
Further, the average particle size of the inorganic filler can be appropriately selected in the range of 50 nm to 20 μm, and the light transmission during exposure and the pattern resolution are improved. Therefore, the average particle size is 50 nm to 2 μm. The average particle size is preferably 1 μm to 20 μm 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.
　また、無機充填材は、組成物における分散性や充填性の向上、硬化物としての機械特性の向上から、カップリング剤等により表面処理することが好ましい。カップリング剤としては、シラン系、チタネート系、アルミネート系およびジルコアルミネート系等のカップリング剤が挙げられ、なかでもシラン系カップリング剤が好ましい。シラン系カップリング剤としては、例えば、ビニルトリメトキシシラン、ビニルトリエトキシシラン等のビニルシラン、３－グリシドキシプロピルトリメトキシシラン、３－グリシドキシプロピルメチルジメトキシシラン、２－（３，４－エポキシシクロヘキシル）エチルトリメトキシシラン等のエポキシシラン、３－メタクリロキシプロピルメチルジメトキシシラン、３－メタクリロキシプロピルトリメトキシシラン等のメタクリルシラン、３－アクリロキシプロピルトリメトキシシラン等のアクリルシラン、３－メルカプトプロピルトリメトキシシラン等のメルカプトシラン、Ｎ－２－（アミノエチル）－３－アミノプロピルメチルジメトキシシラン、Ｎ－２－（アミノエチル）－３－アミノプロピルトリメトキシシラン、Ｎ－フェニル－３－アミノプロピルトリメトキシシラン等のアミノシラン、フェニルトリメトキシシラン等のアルコキシシランが挙げられる。
　そのなかでも、ビニルシラン類、エポキシシラン類、メタクリルシラン類、フェニルトリメトキシシランは、組成物における無機充填材の分散性の向上と保存安定性に優れることから好ましい。また、特に、ビニルシラン類、メタクリルシラン類、アクリルシラン類は、上述の光重合開始剤と併用することでラジカル重合性が得られ、露光部の現像液耐性を向上することができるためより好ましい。
　なお、このようなカップリング剤等により表面処理により有機官能基が付加された無機充填材は、本明細書中において非有機成分として扱う。 Further, 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. Examples of the 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. Examples of 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.
Among them, 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. Further, in particular, 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.
　また、無機充填材の種類に由来する公知慣用の効果は、本発明においても有効である。
　具体的には、硫酸バリウムに由来する耐熱性、耐薬品性付与、シリカに由来する低熱膨張性付与や低誘電正接化、水酸化アルミニウムや水酸化マグネシウムに由来する難燃性付与、アルミナ、窒化ケイ素、窒化ホウ素、窒化アルミニウムに由来する熱伝導性付与、炭酸カルシウムに由来する硬化物表面の粗面化、銀粉末、銅粉末、はんだ粉末に由来する導電性付与等が挙げられる。 Further, known and commonly used effects derived from the type of inorganic filler are also effective in the present invention.
Specifically, 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.
　無機充填材の配合量は、感光性硬化性組成物の有機溶剤を除く成分全量に対して、２０～９３質量％であることが好ましい。この配合量は、組成物の利用目的に応じて適宜調整され、プリント配線板や半導体素子等の保護膜や電気絶縁層、電子部品を固定する接着層の用途であれば、２０～７５質量％が好ましく、電子部品等を封止や内蔵する封止材や部品内蔵層、成型品材料の用途であれば、６０～９３質量％であることが好ましい。 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.
［その他の成分］
　本発明にかかる感光性硬化性組成物は、本発明の効果を阻害しない範囲で、上述した成分以外のその他の成分、例えば、公知慣用の添加物を配合することができる。その他の公知慣用の添加物としては、特に限定されないが、例えば、樹脂及びエラストマー、着色剤、難燃剤、分散剤、消泡剤・レベリング剤、揺変剤などが挙げられる。 [Other ingredients]
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. Other 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.
（樹脂及びエラストマー）
　樹脂及びエラストマーとしては、２５℃で液状ではないエポキシ樹脂、ベンゾオキサジン樹脂、イミド樹脂、マレイミド樹脂、アミド樹脂、不飽和ポリエステル樹脂、アクリレート樹脂、ジアリルフタレート樹脂、シリコーン樹脂、ノルボルネン系樹脂、イソシアネート樹脂、ウレタン樹脂、ベンゾシクロブテン樹脂、ポリアゾメチン樹脂、ブロック共重合体、天然ゴム、ジエン系ゴム、非ジエン系ゴム、熱可塑性エラストマー等が挙げられる。 (Resin and elastomer)
Examples of the resin and elastomer 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.
（着色剤）
　着色剤としては、着色顔料や染料等としてカラーインデックス（Ｃ．Ｉ．；ザ　ソサイエティ　オブ　ダイヤーズ　アンド　カラリスツ（Ｔｈｅ　Ｓｏｃｉｅｔｙ　ｏｆ　Ｄｙｅｒｓ　ａｎｄ　Ｃｏｌｏｕｒｉｓｔｓ）発行）番号が付されているものを挙げることができる。例えば、赤色着色剤としては、モノアゾ系、ジスアゾ系、アゾレーキ系、ベンズイミダゾロン系、ペリレン系、ジケトピロロピロール系、縮合アゾ系、アントラキノン系、キナクリドン系などがある。青色着色剤としては、フタロシアニン系、アントラキノン系などがあり、顔料系はピグメント（Ｐｉｇｍｅｎｔ）に分類されている化合物を使用することができる。これら以外にも、金属置換もしくは無置換のフタロシアニン化合物も使用することができる。緑色着色剤としては、同様にフタロシアニン系、アントラキノン系、ペリレン系がある。これら以外にも、金属置換もしくは無置換のフタロシアニン化合物も使用することができる。黄色着色剤としては、モノアゾ系、ジスアゾ系、縮合アゾ系、ベンズイミダゾロン系、イソインドリノン系、アントラキノン系等がある。白色着色剤としては、ルチル型またはアナターゼ型酸化チタンなどが挙げられる。黒色着色剤としては、カーボンブラック系、黒鉛系、酸化鉄系、チタンブラック、酸化鉄、アンスラキノン系、酸化コバルト系、酸化銅系、マンガン系、酸化アンチモン系、酸化ニッケル系、ペリレン系、アニリン系、硫化モリブデン、硫化ビスマスなどがある。その他、色調を調整する目的で紫、オレンジ、茶色などの着色剤を加えてもよい。 (Colorant)
Examples of the colorant include those having a color index (issued by The Society of Dyers and Colorists) as a color pigment, a dye, or the like. For example, 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. Similarly, as the green colorant, there are phthalocyanine type, anthraquinone type, and perylene type. In addition to these, metal-substituted or unsubstituted phthalocyanine compounds can also be used. Examples of the yellow colorant include monoazo, disazo, condensed azo, benzimidazolone, isoindolinone, anthraquinone and the like. Examples of 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. There are systems, molybdenum sulfide, bismuth sulfide, etc. In addition, a colorant such as purple, orange, or brown may be added for the purpose of adjusting the color tone.
（分散剤）
　分散剤としては、ポリカルボン酸系、ナフタレンスルホン酸ホルマリン縮合系、ポリエチレングリコール、ポリカルボン酸部分アルキルエステル系、ポリエーテル系、ポリアルキレンポリアミン系等の高分子型分散剤、アルキルスルホン酸系、四級アンモニウム系、高級アルコールアルキレンオキサイド系、多価アルコールエステル系、アルキルポリアミン系等の低分子型分散剤等が挙げられ、組成物中の各成分の分散性が向上し、さらに硬化物の機械特性を向上することができる。 (Dispersant)
Examples of the dispersant 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.
（消泡剤・レベリング剤）
　消泡剤・レベリング剤としては、シリコーン、変性シリコーン、鉱物油、植物油、脂肪族アルコール、脂肪酸、金属石鹸、脂肪酸アミド、ポリオキシアルキレングリコール、ポリオキシアルキレンアルキルエーテル、ポリオキシアルキレン脂肪酸エステル等の化合物等が使用でき、塗膜表面の平滑性が向上し、塗膜中のボイドの発生を抑制することができる。 (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.
（揺変剤）
　揺変剤としては、微粒子シリカ、シリカゲル、不定形無機粒子、ポリアミド系添加剤、変性ウレア系添加剤、ワックス系添加剤、有機ベントナイト等が使用でき、塗膜の成膜性が向上し、ダレを抑制することができる。 (Shaking agent)
As the 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.
（難燃剤）
　難燃剤としては、赤燐、燐酸アンモニウム、炭酸アンモニウム、ホウ酸亜鉛、錫酸亜鉛、モリブデン化合物系、臭素化合物系、塩素化合物系、燐酸エステル、含燐ポリオール、含燐アミン、メラミンシアヌレート、メラミン化合物、トリアジン化合物、グアニジン化合物、シリコーンポリマー等が使用でき、硬化物の自己消火性、耐熱性を高いレベルでバランスよく達成できる。 (Flame retardants)
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.
＜ドライフィルム＞
　本発明のドライフィルムは、基材（例えば支持（キャリア）フィルム）上に、本発明の感光性硬化性組成物を塗布後、乾燥して得られる組成物層を有するものである。そして、この組成物層を、目的とする別の基材に接するように熱圧着（ラミネート）して使用される。 <Dry film>
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.
　具体的には、本発明のドライフィルムは、基材（例えば支持（キャリア）フィルム）上に、ブレードコーター、リップコーター、コンマコーター、フィルムコーター等の適宜の方法により本発明の感光性硬化性組成物を均一に塗布し、乾燥して、組成物層を形成し、好ましくはその上にフィルム（いわゆる保護（カバー）フィルム）を積層することにより、製造することができる。保護フィルムと支持フィルムは同一のフィルム材料であっても、異なるフィルムを用いてもよい。 Specifically, 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.
　本発明のドライフィルムにおいて、支持フィルムおよび保護フィルムのフィルム材料としては、ドライフィルムに用いられる公知慣用のものを用いることができる。
　支持フィルムとしては、例えば２～１５０μｍの厚さのポリエチレンテレフタレート等のポリエステルフィルム等の熱可塑性フィルムが用いられる。また、パターン解像性を向上させるため、光透過性に優れる支持フィルムや、組成物層と接する面を粗面化した支持フィルムを用いて、組成物層の表面に支持フィルムの粗面形状を転写する技術を用いることができる。
　保護フィルムとしては、ポリエチレンフィルム、ポリプロピレンフィルム等を使用することができるが、組成物層との接着力が、支持フィルムよりも小さいものが良い。 In the dry film of the present invention, as the film material of the support film and the protective film, known and commonly used films used for the dry film can be used.
As the support film, for example, a thermoplastic film such as a polyester film such as polyethylene terephthalate having a thickness of 2 to 150 μm is used. Further, in order to improve the pattern resolution, 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.
As 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.
　本発明のドライフィルムの組成物層の膜厚は、１～４０μｍが好ましく、１～３０μｍがより好ましい。組成物層の膜厚がこのような範囲にあれば、光照射または加熱した際に、特にナフトキノンジアジド化合物から発生する窒素ガスが組成物層より除去され、良好な塗膜及び硬化膜を形成することができる。 The film thickness of the composition layer of the dry film of the present invention is preferably 1 to 40 μm, more preferably 1 to 30 μm. When the film thickness of the composition layer is within such a range, 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.
　本発明のドライフィルムは、本発明の感光性硬化性組成物からなる組成物層を保護層（外層）とし、本発明の感光性硬化性組成物からナフトキノンジアジド化合物などの化合物（Ｂ）を除いた硬化性組成物を接着層（内層）とした２層構造のドライフィルムにすることができる。
　このような２層構造によれば、保護層の露光部が現像時に直下の接着層の溶解を防ぎ、２層構造でのパターン形成が可能となる。また、化合物（Ｂ）として特にナフトキノンジアジド化合物を用いた場合には、窒素ガスの発生が外層のみとなるため、層内にボイド等を残存させることなく、ドライフィルムとしての高膜厚化が可能となる。
　このような２層構造のドライフィルムでは、保護層の膜厚は、１～４０μｍが好ましく、１～３０μｍがより好ましく、接着層の膜厚は、１～１００μｍが好ましい。 In the dry film of the present invention, 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. Further, when a naphthoquinone diazide compound is used as the compound (B), nitrogen gas is generated only in the outer layer, so that the film thickness of the dry film can be increased without leaving voids or the like in the layer. It becomes.
In such a two-layer structure dry film, the film thickness of the protective layer is preferably 1 to 40 μm, more preferably 1 to 30 μm, and the film thickness of the adhesive layer is preferably 1 to 100 μm.
　２層構造のドライフィルムの製造方法としては、第１の例として、支持フィルム上に、本発明の感光性硬化性組成物を塗布、乾燥して、保護層を形成し、次いで、前記保護層上に、本発明の感光性硬化性組成物からナフトキノンジアジド化合物などの化合物（Ｂ）を除いた硬化性組成物を塗布、乾燥して接着層を形成し、その後、必要に応じて接着層上に保護フィルムを積層して製造する。
　第２の例としては、支持フィルム上に、本発明の感光性硬化性組成物を塗布、乾燥した保護層と、保護フィルム上に、本発明の感光性硬化性組成物からナフトキノンジアジド化合物などの化合物（Ｂ）を除いた硬化性組成物を塗布、乾燥した接着層を各々作製し、保護層と接着層を接するように積層して製造する。 As a method for producing a two-layer structure dry film, as a first example, 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.
As a second example, 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.
　２層構造のドライフィルムの使用方法は、接着層側の保護フィルムを剥離し、この接着層が目的とする別の基材に接するように熱圧着（ラミネート）して使用され、その後の製造工程は、単層のドライフィルムを用いた場合と同じである。 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.
［硬化物］
　本発明の硬化物は、上述した本発明の感光性硬化性組成物またはドライフィルムの組成物層を硬化させたものである。
　本発明の感光性硬化性組成物または組成物層を形成したドライフィルムを用いてパターン形成した硬化物を得る方法としては、例えば、以下の工程を経る方法が挙げられる。 [Cured product]
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.
　まず、塗膜形成工程として、基材上に、感光性硬化性組成物を塗布、乾燥することにより、あるいはドライフィルムから組成物層を転写することにより、乾燥塗膜を形成する。
　ここで、この塗膜形成工程において、基材上に感光性硬化性組成物を塗布する方法としては、従来からの塗布方法、例えば、スピンコーター、バーコーター、ブレードコーター、カーテンコーター、スクリーン印刷機等で塗布する方法、スプレーコーターで噴霧塗布する方法、さらにはインクジェット法等を用いることができる。塗膜を乾燥する方法としては、オーブンまたはホットプレートによる加熱乾燥等の方法が用いられる。また、塗膜の乾燥は、感光性硬化性組成物中の化合物（Ｂ）の熱反応が起こらないような条件下で行う。具体的には、１１０℃以下で１～３０分の条件、好ましくは９０℃以下で１～３０分の条件とする。
　この工程に用いる基材としては、１８０℃以上の硬化温度に耐性を有する基材であれば特に制限はなく、シリコンウエハ等の半導体基材、ガラス繊維に硬化性樹脂を含侵して硬化した基材、ポリイミドフィルム上に予め銅等の回路が形成されたプリント配線板やフレキシブルプリント配線板等の配線基板、金属基板等に広く適用できる。 First, as a coating film forming step, 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.
Here, in 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. As a method for drying the coating film, a method such as heating and drying with an oven or a hot plate is used. Further, the coating film is dried under conditions that do not cause a thermal reaction of the compound (B) in the photosensitive curable composition. Specifically, 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.
　次に、露光工程として、上記工程で基材上に形成した乾燥塗膜に対し、パターンを有するフォトマスクを介して、あるいは直接的に、活性エネルギー線を照射し、パターン露光する。特にドライフィルムによって乾燥塗膜を形成した場合には、支持フィルムを剥離してから露光するか、もしくは、支持フィルム上から露光した後に支持フィルムを剥離することができる。
　ここで、活性エネルギー線としては、化合物（Ｂ）を活性化させることができる波長のものを用いる。具体的には、活性エネルギー線の照射に用いられる露光機の光源として、高圧水銀灯ランプやメタルハライドランプ等を搭載し、３５０～４５０ｎｍの範囲で紫外線を照射する装置であればよく、直接描画（ダイレクトイメージング露光）装置も用いることができる。また、露光量は、膜厚等によって異なるが、一般には１０～１０００ｍＪ／ｃｍ２の範囲内で行う。 Next, as an exposure step, 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. In particular, when the dry coating film is formed by a dry film, 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.
Here, as the active energy ray, one having a wavelength capable of activating the compound (B) is used. Specifically, as a light source of an exposure machine used for irradiating active energy rays, 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.
　次いで、必要に応じてＰＥＢ（ＰＯＳＴ　ＥＸＰＯＳＵＲＥ　ＢＡＫＥ）工程を行う。このＰＥＢ工程は、露光によって化合物（Ｂ）から生成したカルボキシル基および／またはフェノール性水酸基とカルボジイミド基との反応を加熱によって促進する工程である。カルボキシル基および／またはフェノール性水酸基とカルボジイミド基の反応は２５℃程度でも進行するが、ＰＥＢを行うことで、パターン形成性が向上する。
　このＰＥＢ工程では、オーブンまたはホットプレートによる加熱等の方法が用いられる。また、このＰＥＢ工程は、未露光部のナフトキノンジアジド化合物などの化合物（Ｂ）の熱反応が起こらないような条件下の温度で行う。具体的には、１１０℃以下で１～３０分であり、９０℃以下で１～３０分が好ましい。 Then, if necessary, a PEB (POST EXPOSURE BAKE) step is performed. 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.
In this PEB step, a method such as heating with an oven or a hot plate is used. Further, 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.
　次いで、現像工程として、露光工程後またはＰＥＢ工程後の乾燥塗膜を現像液で処理する。これにより、塗膜中の未露光部分を除去して、本発明の感光性硬化性組成物のパターン膜を形成することができる。 Next, as a developing step, 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.
　ここで、この現像工程に用いる方法としては、従来から知られているフォトリソグラフィの現像方法、例えば回転スプレー法、パドル法、超音波処理を伴う浸せき法等の中から任意の方法を選択することができる。現像液としては、上述した有機溶剤を用いることができ、なかでも、石油ナフサ、または石油ナフサとシクロヘキサノンを組み合せた現像液が好ましい。石油ナフサとシクロヘキサノンを混合した現像液では、シクロヘキサノンの比率が高いほど未露光部分の現像性が向上し、石油ナフサの比率が高いほど露光部における現像ダメージが抑制される。石油ナフサとシクロヘキサノンの混合比（石油ナフサ：シクロヘキサノン）としては、９．５：０．５～５：５が好ましく、９：１～７：３がより好ましい。また、必要に応じて、現像液に界面活性剤を適当量添加してもよい。
　この現像工程では、現像液の温度は２０～４０℃、現像時間は１８０秒以内で行う。
　なお、この現像工程では、必要に応じて得られたパターン膜をリンス液により洗浄する。リンス液としては、蒸留水、メタノール、エタノール、イソプロピルアルコール等を単独または組み合わせて用いることができる。 Here, as a method used in this developing step, 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. As 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. In a developer in which petroleum naphtha and cyclohexanone are mixed, 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 (petroleum naphtha: 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.
In this developing step, the temperature of the developing solution is 20 to 40 ° C., and the developing time is 180 seconds or less.
In this developing step, if necessary, 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.
　次いで、上記現像工程にて得られたパターン膜に対し、必要に応じて脱窒素工程を行う。脱窒素の方法としては、塗膜を加熱することにより行うことができる。特に、化合物（Ｂ）としてナフトキノンジアジド化合物には、露光部に残存する未感光のナフトキノンジアジド化合物を熱によって反応させて失活させることができる。
　ここで、脱窒素工程における加熱方法としては、オーブンまたはホットプレートによる加熱等の方法が挙げられる。また、加熱条件は、１２０～１４０℃で１～３０分とする。このような温度範囲であれば、特にナフトキノンジアジド化合物が完全に熱反応して窒素を放出し、かつパターン膜の硬化反応が進行しにくいため、発生した窒素は塗膜中に残存することなく除去される。 Next, 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. In particular, the naphthoquinone diazide compound as compound (B) can be inactivated by reacting the unphotosensitive naphthoquinone diazide compound remaining in the exposed portion with heat.
Here, as 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.
　そして最後に、現像工程または脱窒素工程を終えたパターン膜に対し、硬化工程として、加熱して硬化塗膜（硬化物）を得る。この工程により、カルボジイミド基が架橋反応し、硬化する。
　ここで、この硬化工程における加熱条件は、１８０～２５０℃で３０～９０分であるが、組成物中に環状（チオ）エーテル基を有する化合物を含有する場合には、前記加熱条件の前に１５０～１７０℃で３０～９０分の加熱を加えても良い。 Finally, 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). By this step, the carbodiimide group undergoes a cross-linking reaction and is cured.
Here, 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.
　本発明の感光性硬化性組成物またはドライフィルムは、プリント配線板や半導体素子等の保護膜や電気絶縁層、電子部品等を封止や内蔵する封止材や部品内蔵層、電子部品を固定する接着層等に用いることができ、特に、低誘電率や低誘電正接が要求される高密度配線、高周波信号を扱う電子部品、高温かつ長期の信頼性が要求される車載やロボット用の電子部品に好適である。 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.
　以下、本発明を、実施例を用いてより詳細に説明するが、本発明は下記実施例に限定されるものではない。なお、以下において、「部」および「％」とあるのは、特に断りのない限り、すべて質量基準である。 Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples. In the following, "parts" and "%" are all based on mass unless otherwise specified.
（カルボジイミド基を有する化合物（Ａ１）の合成）
　還流管および撹拌機付き反応容器にジイソシアネートとして、２，４’－ジフェニルメタンジイソシアネート５４質量部、４，４’－ジフェニルメタンジイソシアネート４６質量部との混合物（東ソー製、モノメリックＭＤＩ；ミリオネートＮＭ）、イソシアネート基と反応する官能基を１つ有する化合物として、フェニルイソシアネート１０質量部、カルボジイミド化触媒として、３－メチル－１－フェニル－２－ホスホレン－１－オキシド０．６質量部を入れ、窒素気流下１００℃で２時間撹拌し、赤外吸収（ＩＲ）スペクトル測定による波長２２７０ｃｍ－１前後のイソシアネート基による吸収ピークがほぼ消失したことを確認して、カルボジイミド基を有する化合物（Ａ１）を得た。得られたカルボジイミド基を有する化合物（Ａ１）の重量平均分子量は２，１００、カルボジイミド基当量は２０５ｇ／ｅｑであった。 (Synthesis of compound (A1) having a carbodiimide group)
A mixture of 54 parts by mass of 2,4'-diphenylmethane diisocyanate and 46 parts by mass of 4,4'-diphenylmethane diisocyanate (manufactured by Toso, Monomeric MDI; Millionate NM), isocyanate group in a reaction vessel with a reflux tube and a stirrer. 10 parts by mass of phenylisocyanate is added as a compound having one functional group that reacts with, and 0.6 parts by mass of 3-methyl-1-phenyl-2-phospholene-1-oxide is added as a carbodiimidation catalyst. The mixture was stirred at ° C. for 2 hours , and it was confirmed by infrared absorption (IR) spectrum measurement that the absorption peak due to the isocyanate group having a wavelength of around 2270 cm-1 had almost disappeared, and a compound (A1) having a carbodiimide group was obtained. 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.
（球状シリカの表面処理）
　ＰＭＡ（プロピレングリコールモノメチルエーテルアセテート）５０質量部、アクリルシラン系カップリング剤（信越シリコーン製ＫＢＭ－５１０３（３－アクリロキシプロピルトリメトキシシラン））３質量部を混合した溶液に、球状シリカ（アドマテックス製、ＳＯ－Ｅ２、平均粒子径０．５μｍ）１００質量部を加え、撹拌し均一分散させた後、加熱乾燥して表面処理球状シリカを得た。 (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 μm) 100 parts by mass was added, stirred and uniformly dispersed, and then heat-dried to obtain surface-treated spherical silica.
（球状アルミナの表面処理）
　上記シリカの表面処理において、球状シリカを球状アルミナ（アドマテックス製、Ａ－５０９、平均粒子径１０μｍ）１００量部、カップリング剤をエポキシシラン系カップリング剤（信越シリコーン製ＫＢＭ－４０３（３－グリシドキシプロピルトリメトキシシラン））３質量部に変更した以外はシリカの表面処理と同様にして表面処理球状アルミナを得た。 (Spherical alumina surface treatment)
In the surface treatment of the silica, the spherical silica is 100 parts by volume of spherical alumina (Admatex, A-509, average particle diameter of 10 μm), 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.
（実施例１～１３、比較例１）
　下記の表１に示す配合に従い、各成分を配合し、攪拌機にて撹拌し、必要に応じて３本ロールミルで混練して実施例１～１３、比較例１の感光性硬化性組成物を調製した。なお、表中の配合量は、質量部を示す。 (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.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
＊１：三宝化学研究所社製、ナフトキノンジアジド化合物、ナフトキノンジアジド付加率９３％、生成されるカルボキシル基当量約３８３ｇ／ｅｑ、
Figure JPOXMLDOC01-appb-C000002
 ＊２：新日鉄住金化学社製、ビスフェノールＡ型２官能エポキシ樹脂とビスフェノールＦ型２官能エポキシ樹脂の混合品、エポキシ当量：１６５ｇ／ｅｑ
＊３：ＡＤＥＫＡ製　ジシクロペンタジエン型２官能液状エポキシ樹脂、エポキシ当量１６５ｇ／ｅｑ
＊４：新中村化学製、ＥＯ変性ビスフェノールＡジメタクリレート
＊５：東亜合成製、トリメチロールプロパンＥＯ変性トリアクリレート
＊６：ＩＧＭ　Ｒｅｓｉｎｓ製、モノアシルフォスフィンオキサイド系光重合開始剤
＊７：ＢＡＳＦ製、オキシム系光重合開始剤
＊８：東京化成工業製、コバルト（ＩＩ）アセチルアセトナート
＊９：四国化成製、１－ベンジル－２－フェニルイミダゾール
＊１０：ＪＸＴＧエネルギー製、重質芳香族系石油ソルベントナフサ
＊１１：三協化学製、シクロヘキサノン
＊１２：アドマテックス製、球状シリカ、平均粒子径０．５μｍ、アクリルシラン表面処理
＊１３：アドマテックス製、球状シリカ、平均粒子径５０ｎｍ
＊１４：アドマテックス製、球状アルミナ、平均粒子径１０μｍ、エポキシシラン表面処理 * 1: Manufactured by Sanpo Chemical Research Institute, naphthoquinone diazide compound, naphthoquinone diazide addition rate 93%, carboxyl group equivalent of about 383 g / eq produced,
Figure JPOXMLDOC01-appb-C000002
 * 2: A mixture of bisphenol A type bifunctional epoxy resin and bisphenol F type bifunctional epoxy resin manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent: 165 g / eq
* 3: ADEKA dicyclopentadiene type bifunctional liquid epoxy resin, epoxy equivalent 165 g / eq
* 4: Shin-Nakamura Chemical, EO-modified bisphenol A dimethacrylate * 5: Toa Synthetic, trimethylolpropane EO-modified triacrylate * 6: IGM Resins, monoacylphosphine oxide-based photopolymerization initiator * 7: BASF , Oxime-based photopolymerization initiator * 8: Tokyo Kasei Kogyo, Cobalt (II) acetylacetonate * 9: Shikoku Kasei, 1-benzyl-2-phenylimidazole * 10: JXTG Energy, heavy aromatic petroleum Solvent Nafsa * 11: Sankyo Chemical Co., Ltd., Cyclohexanone * 12: Admatex, spherical silica, average particle size 0.5 μm, acrylic silane surface treatment * 13: Admatex, spherical silica, average particle size 50 nm
* 14: Made by Admatex, spherical alumina, average particle size 10 μm, epoxy silane surface treatment
（保存安定性）
　得られた各実施例および各比較例の感光性硬化性組成物を遮光容器に入れ、２５℃に温度調整された恒温器に２４時間保管した。保管した各組成物を取り出し、ゲル化の有無を確認し、保存安定性を以下の評価基準にて評価した。その結果を表１に示す。
　○：ゲル化しない
　×：ゲル化した (Storage stability)
The obtained photosensitive curable compositions of Examples and Comparative Examples were placed in a light-shielding container and stored in an incubator whose temperature was adjusted to 25 ° C. for 24 hours. Each stored composition was taken out, the presence or absence of gelation was confirmed, and the storage stability was evaluated according to the following evaluation criteria. The results are shown in Table 1.
◯: Not gelled ×: Gelled
（パターン形成性）
　得られた各実施例および各比較例の感光性硬化性組成物を、塗膜形成工程として、銅板上にアプリケータにて乾燥後の塗膜厚が約２５μｍになるように塗布し、オーブンにて８０℃で３０分間乾燥した。次いで、露光工程として、得られた乾燥塗膜に対し、１００μｍのラインパターンを有するフォトマスクを密着させ、紫外線露光装置（（株）オーク製作所製、型式ＨＭＷ－６８０ＧＷ）を用いて露光（露光量１Ｊ／ｃｍ２）した。次いで、ＰＥＢ工程として、露光した塗膜に対し、オーブンにて８０℃で３０分間の加熱処理を行った。次いで、現像工程として、ＰＥＢ工程を終えた乾燥塗膜を、石油ナフサ（カクタスファインＳＦ－０１）９０質量％とシクロヘキサノン１０質量％を混合した現像液に、２０℃で６０秒間浸漬し、揺動させながら現像して、パターン形成した塗膜（パターン膜）を備える銅板（試験片）を作製した。
　得られたパターン膜について、ラインの残存状態を目視にて、現像後の膜厚をマイクロメータにて測定し、下記の評価基準にてパターン形成性を評価した。その結果を表１に示す。
　◎：ラインの欠損がなく、乾燥前の膜厚と現像後の膜厚の差が２μｍ未満
　〇：部分的にラインが欠損、または乾燥前の膜厚と現像後の膜厚の差が２μｍ以上
　×：パターン形成が不可能 (Pattern formation)
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 μm as a coating film forming step, and then placed in an oven. It was dried at 80 ° C. for 30 minutes. Next, as an exposure step, a photomask having a line pattern of 100 μm 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 ). Next, as a PEB step, the exposed coating film was heat-treated in an oven at 80 ° C. for 30 minutes. Next, as a developing step, 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.
With respect to the obtained pattern film, 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 μm. 〇: The line is partially defective, or the difference between the film thickness before drying and the film thickness after development is 2 μm or more. ×: Pattern formation is impossible
（硬化膜（硬化物）の外観）
　上記パターン形成性にて作製した試験片を、脱窒素工程として、オーブンにて１３０℃で３０分間加熱し、さらに硬化工程として、２５０℃に昇温して６０分間加熱処理し、銅板上にパターン形成した硬化膜を備える試験片を得た。
　得られた試験片が備えるパターン形成した硬化膜の外観を目視にて観察し、下記の評価基準にて硬化膜の外観を評価した。その結果を表１に示す。
　○：硬化膜にボイド等の異常が無い
　×：硬化膜にボイド等の異常が有る (Appearance of cured film (cured product))
The test piece produced by the above pattern-forming property is heated in an oven at 130 ° C. for 30 minutes as a denitrification step, and further heated to 250 ° C. for 60 minutes as a curing step, and then patterned on a copper plate. A test piece having the formed cured film was obtained.
The appearance of the patterned cured film contained in the obtained test piece was visually observed, and the appearance of the cured film was evaluated according to the following evaluation criteria. The results are shown in Table 1.
◯: There is no abnormality such as voids in the cured film ×: There is an abnormality such as voids in the cured film
（誘電率及び誘電正接）
　各実施例の組成物を、１８μｍ厚の銅箔の光沢面にアプリケータにて乾燥後の塗膜厚が約２５μｍになるように塗布し、オーブンにて８０℃で３０分間乾燥した。次いで、露光工程として、得られた乾燥塗膜に対し、紫外線露光装置（（株）オーク製作所製、型式ＨＭＷ－６８０ＧＷ）を用いて全面露光（露光量１Ｊ／ｃｍ２）した。次いで、ＰＥＢ工程として、全面露光した塗膜に対し、オーブンにて８０℃で３０分間の加熱処理を行った。次いで、現像工程として、ＰＥＢ工程を終えた乾燥塗膜を、石油ナフサ（カクタスファインＳＦ－０１）９０質量％とシクロヘキサノン１０質量％を混合した現像液に、２０℃で６０秒間浸漬し、揺動させながら現像した。次いで、脱窒素工程として、得られた塗膜をオーブンにて１３０℃で３０分間加熱し、さらに硬化工程として、２５０℃に昇温して６０分間加熱処理し、銅箔に硬化膜を備える試験片を作製した。
　なお、比較例１については、前述の試験にてパターン形成が不可能であったため、上記現像工程を除いて試験片を作製した。 (Permittivity and dielectric loss tangent)
The composition of each example was applied to the glossy surface of a copper foil having a thickness of 18 μm with an applicator so that the coating film thickness after drying was about 25 μm, and dried in an oven at 80 ° C. for 30 minutes. Next, as an exposure step, the obtained dry coating film was fully exposed (exposure amount 1 J / cm 2 ) using an ultraviolet exposure apparatus (manufactured by ORC Manufacturing Co., Ltd., model HMW-680 GW). Next, as a PEB step, the coating film exposed on the entire surface was heat-treated at 80 ° C. for 30 minutes in an oven. Next, as a developing step, 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. Next, as 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.
As for 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.
　このようにして作製した試験片の硬化膜を銅箔から剥離し、硬化膜サンプルとして、ＳＰＤＲ誘電体共振器とネットワークアナライザー（ともにアジレント社製）を用いて、１０ＧＨｚにおける誘電率及び誘電正接を測定し、以下の評価基準にてそれぞれ評価した。その結果を表１に示す。
（誘電率の評価基準）
　◎：３．３未満
　○：３．３以上３．５未満
　×：３．５以上
（誘電正接の評価基準）
　◎：０．０１５未満
　○：０．０１５以上０．０２未満
　×：０．０２以上 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
（耐熱性（ガラス転移温度））
　上記誘電率及び誘電正接の評価にて用いた硬化膜サンプルを、３ｍｍ幅×２０ｍｍ長にカットし、ガラス転移温度の測定用試験片とした。この試験片について、測定装置として日立ハイテクサイエンス社製の「ＴＭＡ／ＳＳ１２０」を用い、昇温速度：５℃／分として測定温度範囲：３０～３５０℃の条件で測定し、以下の評価基準にて耐熱性を評価した。その結果を表１に示す。
　◎：ガラス転移温度が２６０℃以上
　〇：ガラス転移温度が２００℃以上２６０℃未満
　×：ガラス転移温度が２００℃未満 (Heat resistance (glass transition temperature))
The cured film sample used in the evaluation of the dielectric constant and the dielectric loss tangent was cut into a width of 3 mm and a length of 20 mm to prepare a test piece for measuring the glass transition temperature. This test piece was measured using "TMA / SS120" manufactured by Hitachi High-Tech Science Co., Ltd. as a measuring device, with a heating rate of 5 ° C./min and a measurement temperature range of 30 to 350 ° C., and used as the following evaluation criteria. The heat resistance was evaluated. The results are shown in Table 1.
⊚: Glass transition temperature is 260 ° C or higher 〇: Glass transition temperature is 200 ° C or higher and less than 260 ° C ×: Glass transition temperature is less than 200 ° C
　上記表１に示す評価結果から明らかなように、各実施例の感光性硬化性組成物によれば、フォトリソグラフィによるパターン形成が可能であり、その硬化物は、優れた耐熱性（高Ｔｇ）と優れた誘電特性（低誘電率および低誘電正接）を有することが確認された。一方で、比較例１の組成物では、フォトリソグラフィによるパターン形成が不可能であることが確かめられた。 As is clear from the evaluation results shown in Table 1 above, according to the photosensitive curable composition of each example, a pattern can be formed by photolithography, and the cured product has excellent heat resistance (high Tg). It was confirmed that it has excellent dielectric properties (low dielectric constant and low dielectric loss tangent). On the other hand, it was confirmed that the composition of Comparative Example 1 could not form a pattern by photolithography.
（ドライフィルムの作製）
　実施例１１の感光性硬化性組成物を、ＰＥＴフィルム（東レ製、ルミラーＴ６０、厚み２５μｍ）上に、アプリケータにて乾燥後の塗膜厚が２０μｍになるように塗布し、オーブンにて８０℃で３０分間乾燥させて、表２に示した実施例１２の感光性硬化性組成物からなる組成物層を単層として備えるドライフィルムＡを作製した。
　また、実施例１２の感光性硬化性組成物からナフトキノンジアジド化合物を除いた組成物を調製し、かかる組成物を、前記ドライフィルムＡの組成物層上に、さらにアプリケータにて乾燥後の膜厚が４０μｍになるように塗布し、オーブンにて８０℃で３０分間乾燥させて、接着層としての組成物層を形成し、ＰＥＴフィルム上に、実施例１２の組成物からなる組成物層である保護層と接着層とを有する２層構造からなるドライフィルムＢを作製した。 (Making a dry film)
The photosensitive curable composition of Example 11 was applied onto a PET film (manufactured by Toray Industries, Inc., Lumirror T60, thickness 25 μm) with an applicator so that the coating thickness after drying was 20 μm, 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.
Further, 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. It is applied to a thickness of 40 μm and dried in an oven at 80 ° C. for 30 minutes to form a composition layer as an adhesive layer, and a composition layer composed of the composition of Example 12 is formed on a PET film. A dry film B having a two-layer structure having a certain protective layer and an adhesive layer was produced.
　このようにして作製したドライフィルムＡおよびＢを銅板上にＰＥＴフィルムが外側になるように設置し、真空ラミネーター（ニッコーマテリアルズ製ＣＶＰ－３００）を用いて加圧力：０．４ＭＰａ、１１０℃、１分、真空度：３ｈＰａの条件で加熱ラミネートした。次いで、ＰＥＴフィルムを剥離し、上述したパターン形成性と硬化物の外観の評価試験と同様の方法にて、パターン形成した塗膜を備える試験片及びパターン形成した硬化膜を備える試験片を作製し、パターン形成性と硬化物の外観を評価した。その結果を表２に示す。 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. Next, 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.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　上記表２に示す評価結果から明らかなように、本発明の感光性硬化性組成物は、単層のドライフィルム化および２層構造のドライフィルム化が可能であり、これらのドライフィルムによれば、フォトリソグラフィによるパターン形成と、外観にボイド等の異常がなく、厚膜の硬化物も得られることが確かめられた。 As is clear from the evaluation results shown in Table 2 above, 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.
　１０ａ　液状判定用試験管
　１０ｂ　温度測定用試験管
　１１　標線（Ａ線）
　１２　標線（Ｂ線）
　１３ａ，１３ｂ　ゴム栓
　１４　温度計
  10a Liquid judgment test tube 10b Temperature measurement test tube 11 Marked line (A line)
12 Mark line (B line)
13a, 13b Rubber stopper 14 Thermometer

Claims (7)

  1. 　（Ａ）カルボジイミド基を有する化合物と、
    　（Ｂ）光によってカルボキシル基および／またはフェノール性水酸基を生成する化合物と、を含むことを特徴とする感光性硬化性組成物。     (A) A compound having a carbodiimide group and
    (B) A photosensitive curable composition comprising (B) a compound that produces a carboxyl group and / or a phenolic hydroxyl group by light.
  2. 　前記（Ｂ）光によってカルボキシル基および／またはフェノール性水酸基を生成する化合物が、ナフトキノンジアジド化合物であることを特徴とする請求項１に記載の感光性硬化性組成物。 The photosensitive curable composition according to claim 1, wherein the compound that produces a carboxyl group and / or a phenolic hydroxyl group by the light (B) is a naphthoquinone diazide compound.
  3. 　組成物中にカルボキシル基および／またはフェノール性水酸基を有する化合物を実質的に含まないことを特徴とする請求項１または２に記載の感光性硬化性組成物。 The photosensitive curable composition according to claim 1 or 2, wherein the composition does not substantially contain a compound having a carboxyl group and / or a phenolic hydroxyl group.
  4. 　前記（Ａ）カルボジイミド基を有する化合物は、有機溶剤を除く組成物の有機成分中に５０～９９質量％の割合で配合されていることを特徴とする請求項１～３のいずれか一項に記載の感光性硬化性組成物。 The compound having a 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, according to any one of claims 1 to 3. The photosensitive curable composition according to the above.
  5. 　基材上に、請求項１～４のいずれか一項に記載の感光性硬化性組成物を塗布、乾燥してなる組成物層を備えるドライフィルム。 A dry film comprising a composition layer obtained by applying and drying the photosensitive curable composition according to any one of claims 1 to 4 on a base material.
  6. 　請求項１～４のいずれか一項に記載の感光性硬化性組成物、または、請求項５に記載のドライフィルムの組成物層を硬化してなる硬化物。 The photosensitive curable composition according to any one of claims 1 to 4, or a cured product obtained by curing the composition layer of the dry film according to claim 5.
  7. 　請求項６に記載の硬化物を備える電子部品。
          An electronic component comprising the cured product according to claim 6.
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