TW201609911A - Curable resin composition, dry film and printed circuit board - Google Patents

Abstract

The invention provides a curable resin composition, a dry film and a printed circuit board, and specifically provides a curable resin composition, which cannot degrade various characteristics of resolution, adhesiveness, film hardness, soldering resistance thermal performance and the like, and a cured material of which displays a low dielectric constant and a low dielectric loss angel tangent and displays stable insulation resistance, a dry film using the same and a printed circuit board. The curable resin composition contains at least any one of a carboxyl-containing resin and a perovskite-type compound; and the perovskite-type compound contains calcium carbonate, strontium titanate, barium zirconate, calcium zirconate, strontium zirconate and a composite oxide which takes the calcium carbonate, the strontium titanate, the barium zirconate, the calcium zirconate and the strontium zirconate as main components.

Description

Curable resin composition, dry film and printed circuit board

The present invention relates to a curable resin composition, a dry film, and a printed circuit board, and more particularly to a preferred curable resin composition for use in a substrate material which is advantageous for high-frequency communication, a dry film using the same, and a printed circuit board.

In general, a printed circuit board is used as an interlayer insulating material or a solder resist material based on heat resistance or electrical insulating properties, and has been widely used as a main component of a modified epoxy acrylate compound or an epoxy resin, and further A resin composition containing an additive component such as a filler.

However, the cured product of the conventional resin composition used for the substrate materials has a dielectric constant of about 4.0 and a dielectric tangent of about 0.03. When the wiring board using the resin composition as a substrate material is communicated in a high frequency field, There is an inevitable delay in signal transmission or loss of signal.

In contrast, in order to reduce the dielectric constant and dielectric tangent of the board material, a circuit board material using a filler having a small dielectric constant or dielectric tangent has been proposed. For example, a solder resist having a spherical porous filler having a small dielectric constant or a dielectric tangent is proposed (see Patent Document 1).

However, even if the dielectric porosity or dielectric tangent is small, the spherical porous The quality of the filler, in the end, still can not obtain sufficient signal characteristics, but there is still room for improvement.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] International Publication No. 2006/008995

The present invention has been made in view of the problems of the prior art described above, and its main object is to provide deterioration of properties such as resolution, adhesion, coating film hardness, and solder heat resistance, and a cured product having a low dielectric constant and A low dielectric tangent and a hardenable resin composition exhibiting a stable insulating resistance.

Further, another object of the present invention is to provide a printed circuit board comprising a dry film made of the curable resin composition and a cured film having a solder resist or the like formed using the above.

As a result of active research to achieve the above object, the present inventors have found that a composite oxide mainly composed of calcium titanate, barium titanate, strontium zirconate, calcium zirconate, strontium zirconate, and the like is used. At least one of the formed perovskite-type compounds was used as a filler, and it was unexpectedly found that the dielectric constant tangent was greatly reduced while maintaining the low dielectric constant, and thus the present invention having the following main constitution was completed.

That is, the curable resin composition of the present invention is characterized by containing a carboxyl group-containing resin and consisting of calcium titanate, barium titanate, barium zirconate, calcium zirconate, barium zirconate, and the like as main components. At least one of the perovskite-type compounds formed by the composite oxide.

Here, the curable resin composition of the present invention preferably further contains at least one selected from the group consisting of a photocurable component and a thermosetting component.

The dry film of the present invention is obtained by applying the curable resin composition onto a film and drying it.

The cured product of the present invention is obtained by curing the curable resin composition or the dry film.

The printed wiring board of the present invention has a cured film obtained by curing the curable resin composition or the dry film.

According to the present invention, it is possible to provide deterioration of properties such as resolution, adhesion, coating film hardness, and solder heat resistance, and the cured material has a low dielectric constant and a low dielectric tangent, and exhibits a hardening property of a stable insulating resistance. Resin composition and dry film.

As a result, even when communication is performed in the high frequency field, delay in signal transmission or signal loss can be suppressed, and it can be effectively used as a substrate material for facilitating high frequency communication.

Further, according to the present invention, it is possible to provide a printed circuit board having a hardened film having a low dielectric constant and a low dielectric tangent and exhibiting a stable insulating resistance.

Hereinafter, the present invention will be described in detail.

The curable resin composition of the present invention is characterized by comprising a carboxyl group-containing resin and a composite oxide mainly composed of calcium titanate, barium titanate, barium zirconate, calcium zirconate, barium zirconate, and the like. At least one of the obtained perovskite-type compounds.

[Carboxyl group-containing resin]

As the carboxyl group-containing resin constituting the curable resin composition of the present invention, a conventional carboxyl group-containing resin can be used. In addition to the presence of a carboxyl group, the resin composition can be used as a thermosetting component in addition to the alkali imaging property of the resin composition.

Further, when functioning as a photocurable component, it is preferred to have an ethylenically unsaturated bond in addition to a carboxyl group, but it is also possible to use only a carboxyl group-containing resin having no ethylenically unsaturated bond as the carboxyl group-containing group of the present invention. Resin.

In addition, when a carboxyl group-containing resin having no ethylenic unsaturated double bond is used, in order to make the composition photocurable, a photosensitive compound having an ethylenically unsaturated group in a molecule to be described later is used in combination with light curing. Polymerizable monomer).

The carboxyl group-containing resin is particularly preferably a carboxyl group-containing resin which does not use an epoxy resin as a starting material. The carboxyl group-containing resin which does not use an epoxy resin as a starting material is excellent in insulation reliability and has a small number of hydroxyl groups because the halide ion content is extremely small, so that the increase in dielectric constant can be further suppressed.

The specific example of the carboxyl group-containing resin is preferably a compound (any one of an oligomer and a polymer) as listed below.

(1) A reaction product obtained by reacting a compound having two or more phenolic hydroxyl groups in one molecule with an alkylene oxide such as ethylene oxide or propylene oxide, and a single unsaturated group such as (meth)acrylic acid A carboxyl group-containing photosensitive resin obtained by reacting a carboxylic acid with a polybasic acid anhydride such as maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride or adipic acid.

(2) a reaction product obtained by reacting a compound having two or more phenolic hydroxyl groups in one molecule with a cyclic carbonate compound such as ethyl acetate or propylene carbonate, and a monocarboxylic acid containing an unsaturated group. The reaction is carried out to obtain a carboxyl group-containing photosensitive resin obtained by reacting the obtained reaction product with a polybasic acid anhydride.

(3) A diisocyanate compound such as an aliphatic diisocyanate, a branched aliphatic diisocyanate, an alicyclic diisocyanate or an aromatic diisocyanate, and a polycarboxylate polyol, a polyether polyol, or a polyester compound Amine obtained by polyaddition reaction of a diol compound such as an alcohol, a polyolefin-based polyol, an acrylic polyol, a bisphenol A-based alkylene oxide adduct diol, or a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group The terminal carboxyl group-containing urethane resin obtained by reacting the terminal of the urethane resin with an acid anhydride.

(4) A carboxyl group-containing amine group obtained by a polyaddition reaction of a diisocyanate, a carboxy group-containing diol compound such as dimethylolpropionic acid or dimethylolbutanoic acid, and a diol compound In the synthesis of the acid ester resin, a terminal (meth) propyl group having a hydroxyl group and one or more (meth) acrylonitrile groups in a molecule such as a hydroxyalkyl (meth) acrylate is added. A carboxylic acid-containing photosensitive urethane resin.

(5) adding isophorone diisocyanate to a synthesis of a carboxyl group-containing urethane resin obtained by a polyaddition reaction of a diisocyanate, a diol compound containing a carboxyl group, and a diol compound A (meth)acrylated carboxyl group-containing sensitization of a terminal having one isocyanate group and one or more (meth) acrylonitrile groups in a molecule such as a pentaerythritol triacrylate or the like. Amino urethane resin.

(6) A carboxyl group obtained by copolymerization of an unsaturated carboxylic acid such as (meth)acrylic acid with a compound containing an unsaturated group such as styrene, α-methylstyrene, a lower alkyl (meth)acrylate or an isobutylene. Resin.

(7) reacting a bifunctional or higher polyfunctional epoxy resin with (meth)acrylic acid, and adding phthalic anhydride, tetrahydrophthalic anhydride, and hexahydrogen to the hydroxyl group present in the side chain A photosensitive resin containing a carboxyl group formed by a dibasic acid anhydride such as phthalic anhydride.

(8) A carboxyl group-containing photosensitive resin obtained by adding a compound having a cyclic ether group and a (meth) acrylonitrile group in one molecule to the carboxyl group-containing resin of the above (1) to (7).

Further, in the present specification, the term "(meth)acrylate" is a generic term for acrylate, methacrylate, and the like, and the same applies to other similar expressions.

The carboxyl group-containing resin as described above is due to the backbone. The polymer has a large number of free carboxyl groups in its side chain, so it can be developed with an aqueous alkaline solution.

Further, the acid value of the carboxyl group-containing resin is preferably in the range of 40 to 150 mhKOH/g, more preferably 40 to 130 mgKOH/g. Carboxyl-containing resin When the acid value is within this range, the alkali image formation becomes easy, the dissolution of the exposed portion due to the developing liquid is suppressed, the wire is not fined to the extent necessary, and the film is not dissolved and peeled off by the developing solution, and the normal pattern can be performed. Depiction.

Further, the weight average molecular weight of the above carboxyl group-containing resin varies depending on the resin skeleton, but it is usually preferably from 2,000 to 150,000, more preferably from 5,000 to 100,000. When the weight average molecular weight is within this range, it is excellent in tact-free performance, and the coating film after exposure is excellent in moisture resistance, and is excellent in resolution, developability, and storage stability.

The compounding amount of the carboxyl group-containing resin is preferably from 10 to 60% by mass, more preferably from 20 to 50% by mass, based on the total amount of the composition. When the amount of the carboxyl group-containing resin is within this range, the strength of the coating film is not lowered, and the viscosity is not increased and the workability is lowered.

[Perovskite compound]

The perovskite-type compound constituting the curable resin composition of the present invention is composed of calcium titanate, barium titanate, barium zirconate, calcium zirconate, barium zirconate, and a composite oxide containing the main component thereof. . By using the filler formed of at least one of the perovskite-type compounds, the properties such as resolution, adhesion, film hardness, and solder heat resistance are unexpectedly deteriorated, and can be kept low on the one hand. The dielectric ratio, on the one hand, causes the dielectric tangent to drop drastically and exhibits a stable insulation resistance.

The perovskite type compound preferably has an average particle diameter of 0.05 to 0.5 μm. When the average particle diameter is within this range, it is uniformly dispersed in the coating film to obtain stable coating film properties.

Further, in order to obtain sufficient wettability for an organic compound such as a resin, the perovskite-type compound may be subjected to surface treatment using, for example, a coupling agent such as amino decane or decyl decane or vinyl decane.

The perovskite compound is composed of calcium titanate, barium titanate, barium zirconate, calcium zirconate, barium zirconate, and a composite oxide containing the same as the main component, as long as the desired dielectric is obtained. The rate, the dielectric tangent, and the satisfactory characteristics as a printed circuit board can be used without any particular limitation. Among these, calcium titanate, barium titanate, calcium zirconate, strontium zirconate or a composite oxide containing the main component as a main component is preferably used.

Commercially available products are ST-03, CT-03, SZ-03, CZ-03, and the like manufactured by Sigma Chemical Industry Co., Ltd.

The blending amount of the perovskite-type compound is preferably from 50 to 300 parts by mass based on 100 parts by mass of the carboxyl group-containing resin. More preferably 50 to 250 parts by mass. When the amount of the perovskite-type compound is within this range, various characteristics can be maintained and a more excellent low dielectric tangent of the cured product can be obtained.

The curable resin composition of the present invention further preferably contains at least one selected from the group consisting of a photocurable component and a thermosetting component.

[Photohardenable component]

The photocurable component used in the curable resin composition of the present invention may be a photosensitive compound (photopolymerizable monomer) having an ethylenically unsaturated group or a photopolymerization initiator, a photoinitiator, or a sensitizer. .

The compound having an ethylenically unsaturated group used in the curable resin composition of the present invention is photohardened by irradiation with an active energy ray to harden the present invention. The coating film of the chemical resin composition is insoluble in an aqueous alkaline solution or functions as an insoluble person.

As the compound, conventionally used polyester (meth) acrylate, polyether (meth) acrylate, urethane (meth) acrylate, carbonate (meth) acrylate, epoxy (A) can be used. Specific examples of the acrylate or the like include hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate; ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol; Alcohol diacrylates; N,N-dimethyl decylamine, N-methylol acrylamide, N,N-dimethylaminopropyl acrylamide and other acrylamides; acrylic acid N, Aminoalkyl acrylates such as N-dimethylaminoethyl ester and N,N-dimethylaminopropyl acrylate; hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, gin-hydroxyethyl a polyvalent acrylate such as a polyhydric acid such as isocyanurate or such an ethylene oxide adduct, a propylene oxide adduct or an ε-caprolactone adduct; phenoxy acrylate, double a polyvalent acrylate such as phenol A diacrylate and an ethylene oxide adduct of such a phenol or a propylene oxide adduct; glycerol diglycidyl ether, glycerol a polyvalent acrylate of a glycidyl ether such as triglycidyl ether, trimethylolpropane triglycidyl ether or triglycidyl isocyanurate; not limited to the above, which may be mentioned as a polyether polyol or a polycarbonate Polyols such as ester diols, hydroxyl-terminated polybutadienes, polyester polyols, etc. are directly acrylated, or acrylates and melamine acrylates obtained by acylation of diisocyanates with urethanes, and / Or corresponding to each methacrylate of the above acrylate or the like.

Further, examples thereof include a cresol novolak type epoxy resin, and the like. An epoxy acrylate resin obtained by reacting a polyfunctional epoxy resin with acrylic acid, or a hydroxyl group of an epoxy acrylate resin and a hydroxy acrylate such as pentaerythritol triacrylate or a diisocyanate such as isophorone diisocyanate An epoxy urethane acrylate compound obtained by reacting a semi-carbamate compound. These epoxy acrylate-based resins can improve the photocurability without lowering the dryness of the touch.

The compounding amount of the compound having an ethylenically unsaturated group is preferably from 1 to 50 parts by mass, more preferably from 5 to 40 parts by mass, per 100 parts by mass of the carboxyl group-containing resin. When the amount of the compound is within this range, the photocurability is excellent, and the alkali image after irradiation with the active energy ray is more likely to form a pattern.

The photopolymerization initiator used in the curable resin composition of the present invention can be used by a conventional one, and for example, an oxime ester photopolymerization initiator having an oxime ester group or an α-aminoacetophenone photopolymerization can be used. A starter, a fluorenylphosphine oxide-based photopolymerization initiator, a titanocene photopolymerization initiator, and the like.

Commercially available products of the above-mentioned oxime ester-based photopolymerization initiators are CGI-325, Irgacure OXE01, Irgacure OXE02 manufactured by BASF Corporation of Japan, N-1919 manufactured by ADEKA Co., Ltd., NCI-831, and the like.

The above α-aminoacetophenone photopolymerization initiator is specifically exemplified as 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinylacetone-1, 2-benzyl 2-dimethylamino-1-(4-morpholinylphenyl)-butan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl] 1-[4-(4-morpholinyl)phenyl]-1-butanone, N,N-dimethylaminoacetophenone, and the like. Commercial products can be used in Japan Irgacure 907, Irgacure 369, Irgacure 379, etc. manufactured by BASF Corporation.

The above-mentioned fluorenylphosphine oxide-based photopolymerization initiator is specifically exemplified by 2,4,6-trimethylbenzimidyldiphenylphosphine oxide and bis(2,4,6-trimethylbenzylidene). ——Phenylphosphine oxide, bis(2,6-dimethoxybenzylidene)-2,4,4-trimethyl-pentylphosphine oxide, and the like. Commercially available products are listed as Lucirin TPO, Irgacure 819, and the like manufactured by BASF Corporation of Japan.

The above-mentioned titanocene-based photopolymerization initiator is specifically exemplified by bis(cyclopentadienyl)-diphenyltitanium, bis(cyclopentadienyl)-dichlorotitanium, bis(cyclopentadienyl). -bis(2,3,4,5,6-pentafluorophenyl)titanium, bis(cyclopentadienyl)-bis(2,6-difluoro-3-(pyrrol-1-yl)phenyl) Titanium, etc. Commercially available products are Irgacure 784 manufactured by BASF Corporation of Japan.

The photoinitiator and the sensitizer used in the curable resin composition of the present invention may be exemplified by a benzoin compound, an acetophenone compound, an anthraquinone compound, a thioxanthone compound, an acetal compound, or a benzophenone compound. , tertiary amine compounds, and xanthone compounds. Among them, a thioxanthone compound and a tertiary amine compound are preferred. In particular, a thioxanthone compound is preferred in terms of deep hardenability.

The aforementioned thioxanthone compounds are specifically exemplified as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone. In the case of the commercial product, KAYACURE DETX-S manufactured by Nippon Kayaku Co., Ltd., or the like can be used.

The above tertiary amine compound is specifically exemplified as an ethanolamine compound, A compound having a dialkylaminobenzene structure, commercially available as 4,4'-dimethylaminobenzophenone (NISSOKUA MABP manufactured by Japan Soda Co., Ltd.), 4,4'-diethylamino group Dialkylaminobenzophenone, 7-(diethylamino)-4-methyl-2H-1-benzopyran-2-one, such as benzophenone (EAB manufactured by Hodogaya Chemical Co., Ltd.) A dialkylamine-based coumarin compound such as (7-(diethylamino)-4-methylcoumarin) or ethyl 4-dimethylaminobenzoate (KAYAKUA EPA manufactured by Nippon Kayaku Co., Ltd.) , 2-Dimethylaminobenzoic acid ethyl ester (Quantacure DMB manufactured by International Biosynthesis Co., Ltd.), 4-dimethylaminobenzoic acid (n-butoxy)ethyl ester (Quantacure BEA manufactured by International Biosynthesis Co., Ltd.) , p-Dimethylaminobenzoic acid isoamyl ethyl ester (KAYACURE DMBI manufactured by Nippon Kayaku Co., Ltd.), 4-dimethylaminobenzoic acid 2-ethylhexyl ester (Esolol 507 manufactured by Van Dyk Co., Ltd.), and the like.

These photopolymerization initiators, photoinitiating aids, and sensitizers may be used singly or in combination of two or more.

The total amount of the photopolymerization initiator, the photoinitiating aid, and the sensitizer is preferably 35 parts by mass or less based on 100 parts by mass of the carboxyl group-containing resin. When the total amount of the photopolymerization initiator, the photoinitiating aid, and the sensitizer is within this range, light is not absorbed by these, and the deep hardenability can be improved.

[thermosetting component]

The thermosetting component used in the curable resin composition of the present invention serves to impart heat resistance.

The thermosetting component used in the present invention may be a melamine resin or a benzene. An amine resin such as an anthracene resin, a polyisocyanate compound, a protected isocyanate compound, a cyclic carboxylate compound, a polyfunctional epoxy compound, a polyfunctional oxetane compound, an episulfide resin, a melamine derivative, a benzoquinone derivative A thermosetting resin conventionally used, such as a compound, a bismaleimide, an oxazine compound, an oxazoline compound, or a carbodiimide compound. It is preferably a thermosetting component having a plurality of cyclic ether groups or cyclic thioether groups (hereinafter simply referred to as "cyclic (thio) ether groups") in the molecule.

The thermosetting component having a plurality of cyclic (thio)ether groups in the molecule is any one or two of a cyclic ether group having a plurality of 3, 4 or 5 membered rings or a cyclic thioether group in the molecule. The compound of the group is exemplified by, for example, a compound having a plurality of epoxy groups in the molecule, that is, a polyfunctional epoxy compound, and a compound having a plurality of oxetanyl groups in the molecule, that is, a polyfunctional oxetane compound. A compound having a plurality of thioether groups in the molecule, that is, an episulfide resin or the like.

As the polyfunctional epoxy compound, there are listed jER 828, jER 834, jER 1001, jER 1004 manufactured by Mitsubishi Chemical Corporation, EHPE 3150 manufactured by Daicel Chemical Industry Co., Ltd., Epiclon 840, Epiclon 850, Epiclon 1050, Epiclon 2055 manufactured by DIC Corporation. EPOOT YD-011, YD-013, YD-127, YD-128 manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., DER317, DER331, DER661, DER664 manufactured by Dow Chemical Co., Ltd., Araldite 6071 of BASF Corporation of Japan, Araldite 6084, Araldite GY250, Araldite GY260, Sumi-epoxy ESA-011, ESA-014, ELA-115, ELA-128 manufactured by Sumitomo Chemical Industries, Inc., manufactured by Asahi Kasei Industrial Co., Ltd. AER330, AER331, AER661, AER664, etc. (both trade names) of bisphenol A epoxy resin; jER YL 903 manufactured by Mitsubishi Chemical Corporation, Epiclon 152, Epiclon 165 manufactured by DIC Corporation, Nippon Steel & Sumitomo EPOTOT YDB-400, YDB-500 manufactured by Chemical Company, DER542 manufactured by Dow Chemical Co., Ltd., Araldite 8011 manufactured by BASF Corporation of Japan, Sumi-epoxy ESB-400 and ESB-700 manufactured by Sumitomo Chemical Co., Ltd., manufactured by Asahi Kasei Industrial Co., Ltd. AER711, AER714, etc. (both trade names) brominated epoxy resin; jER 152, jER 154 manufactured by Mitsubishi Chemical Corporation, DEN431, DEN438 manufactured by Dow Chemical Co., Ltd., Epiclon N-730 manufactured by DIC Corporation, Epiclon N-770, Epiclon N-865, EPOTOT YDCN-701, YDCN-704 manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., Araldite ECN1235, Araldite ECN1273, Araldite ECN1299, Araldite XPY307 manufactured by BASF Corporation of Japan, manufactured by Nippon Kayaku Co., Ltd. EPPN-201, EOCN-1025, EOCN-1020, EOCN-104S, RE-306, NC-3000, Sumi-epoxy ESCN-195X, ESCN-220, ECN-235, ECN-299, etc. manufactured by Sumitomo Chemical Industries, Ltd. ( All are trade names) Aldehyde type epoxy resin; Epiclon 830 manufactured by DIC Corporation, jER 807 manufactured by Mitsubishi Chemical Corporation, ETOPOT YDF-170, YDF-175, YDF-2004 manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., Araldite XPY306 manufactured by BASF Corporation of Japan Bisphenol F-type epoxy resin (both trade names); hydrogenated bisphenol A epoxy resin such as EPOTOT ST-2004, ST-2007, ST-3000 (trade name) manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd. ; jER 604 manufactured by Mitsubishi Chemical Corporation, Nippon Steel & Sumitomo EPOTOT YH-434 manufactured by Chemical Company, Araldite MY720 manufactured by BASF Corporation of Japan, glycidylamine type epoxy resin of Sumi-epoxy ELM-120 (all trade names) manufactured by Sumitomo Chemical Industries Co., Ltd.; manufactured by BASF Corporation of Japan Araldite CY-350 (trade name) and other uranium-type epoxy resin; Celloxide 2021 manufactured by Dicel Chemical Industry Co., Ltd., Araldite CY175, CY179, etc. (all trade names) manufactured by BASF Corporation of Japan, alicyclic epoxy Resin; YL-933 manufactured by Mitsubishi Chemical Corporation, TEN, EPPN-501, EPPN-502, etc. (all trade names) manufactured by Dao Chemical Co., Ltd. (triester phenylmethane type epoxy resin; YL- manufactured by Mitsubishi Chemical Corporation 6056, YX-4000, YL-6121 (all trade names), etc., bis xylenol type or biphenol type epoxy resin or a mixture thereof; EBPS-200 manufactured by Nippon Kayaku Co., Ltd., manufactured by ADEKA Industries Co., Ltd. EPX-30, bisphenol S type epoxy resin such as EXA-1514 (trade name) manufactured by DIC Corporation; bisphenol A novolac type epoxy resin such as jER 157S (trade name) manufactured by Mitsubishi Chemical Corporation; Mitsubishi Chemical Corporation YL-931 manufactured by the company, manufactured by BASF Corporation of Japan Araldite 163 (all trade name) tetraphenyl phenyl ethane type epoxy resin; Araldite PT810 (trade name) manufactured by BASF Corporation of Japan, and heterocyclic ring of TEPIC (registered trademark) manufactured by Nissan Chemical Industries, Ltd. Oxygen resin; diglycidyl phthalate resin such as Blenmer (registered trademark) DGT manufactured by Nippon Oil Co., Ltd.; tetraglycidyl xylene decyl ethane resin such as ZX-1063 manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.; ESN-190, ESN-360 manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., epoxy resin containing naphthalene based on HP-4032, EXA-4750, EXA-4700 manufactured by DIC Corporation; Epoxy resin having a dicyclopentadiene skeleton such as HP-7200 or HP-7200H; glycidyl methacrylate copolymer epoxy resin such as CP-50S and CP-50M manufactured by Nippon Oil Co., Ltd.; Copolymerized epoxy resin of hexylmalanimide and glycidyl methacrylate; epoxy modified polybutadiene rubber derivative (for example, PB-3600 manufactured by Dicel Chemical Industry, etc.), CTBN modification Epoxy resin (for example, YR-102, YR-450, etc. manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), etc., but is not limited thereto. These epoxy resins may be used singly or in combination of two or more.

The aforementioned polyfunctional oxetane compound is exemplified by bis[(3-methyl-3-oxetanylmethoxy)methyl]ether, bis[(3-ethyl-3-oxetanylmethoxy) )methyl]ether, 1,4-bis[(3-methyl-3-oxetanylmethoxy)methyl]benzene, 1,4-bis[(3-ethyl-3-oxetanyl) Oxy)methyl]benzene, (3-methyl-3-oxetanyl)methyl acrylate, (3-ethyl-3-oxetanyl)methyl acrylate, methacrylic acid (3- Methyl-3-oxetanyl)methyl ester, (3-ethyl-3-oxetanyl)methyl methacrylate or a polyfunctional oxygen heterocycle such as an oligomer or copolymer thereof Butanes, and oxetane and novolac resins, poly(p-hydroxystyrene), CALDO bisphenols, calixarenes, resorcinol calixarenes, or sesquiterpenes An etherified product of a resin having a hydroxyl group such as oxyalkylene. Further, a copolymer of an unsaturated monomer having an oxetane ring and an alkyl (meth)acrylate is exemplified.

The compound having a plurality of cyclic thioether groups in the above molecule is exemplified by bisphenol A type episulfide resin YL7000 manufactured by Mitsubishi Chemical Corporation. Also, it is also possible to use the same synthesis method to sulphur Substituting an epoxy sulfide resin such as an oxygen atom of an epoxy group of a novolac type epoxy resin.

The blending amount in the case where the thermosetting component having a plurality of cyclic (thio)ether groups in the molecule is blended is preferably from 0.1 to 2.0 equivalents, more preferably from 0.2 to 1.6 equivalents, per equivalent of the carboxyl group in the composition. When the amount of the thermosetting component having a plurality of cyclic (thio)ether groups in the molecule is within this range, the thermosetting reaction of the carboxyl group and the cyclic (thio)ether group proceeds sufficiently, and the solder heat resistance and the like can be sufficiently obtained. The characteristics, and further the strength and preservation stability of the coating film become better.

When a thermosetting component having a plurality of cyclic (thio)ether groups in the above molecule is used, it is preferred to contain a thermosetting catalyst. The thermosetting catalysts are exemplified by, for example, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyano group. An azole derivative such as ethyl-2-phenylimidazole or 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole; dicyanodiamine, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-N,N-dimethylbenzyl An amine compound such as a base amine, an anthracene compound such as diammonium adipate or diterpene sebacate; a phosphorus compound such as triphenylphosphine or the like. In addition, it is listed as, for example, 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (all trade names of imidazole-based compounds) manufactured by Shikoku Chemical Industry Co., Ltd., and U-CAT 3503N, U manufactured by SAN-APRO Co., Ltd. -CAT 3502T (both trade names of protected isocyanate compounds of dimethylamine), DBU, DBN, U-CATSA102, U-CAT5002 (both bicyclic guanidine compounds and salts thereof). In particular, it is not limited to these, if The thermosetting catalyst of the epoxy resin and the oxetane compound or the reaction of the epoxy group or the oxetane group with the carboxyl group may be used singly or in combination of two or more. Further, guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methylpropenyloxyethyl-S-triazine, 2- Vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine. Isocyanuric acid adduct, 2,4-diamino-6-methylpropenyloxyethyl-S-triazine. The S-triazine derivative such as an isocyanuric acid addition product is preferably used in combination with the above-mentioned thermosetting catalyst as a compound having a function as a tackifier.

The amount of the thermosetting catalyst is sufficient in a usual amount, and is, for example, preferably 0.1 to 20 parts by mass, more preferably 0.5 to 15.0 parts by mass, per 100 parts by mass of the carboxyl group-containing resin.

In the curable resin composition of the present invention, an adhesion promoter can be used to improve the adhesion between the layers or the adhesion between the photosensitive resin layer and the substrate. Specific examples include benzimidazole, benzoxazole, benzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 3-morpholinylmethyl 1-phenyl-triazole-2-thione, 5-amino-3-morpholinylmethyl-thiazole-2-thione, 2-mercapto-5-methylthio-thiadiazole, triazole , tetrazole, benzotriazole, carboxybenzotriazole, benzotriazole containing an amine group, vinyl triazine, decane coupling agent, and the like.

[Other ingredients]

The curable resin composition of the present invention is preferably formulated with Neuburg Siliceous Earth particles as other additive components.

The Novoloy bauxite particles are a natural combination of Sillitin and Sillikolloid, and have a structure in which spherical cerium oxide and platy kaolin are closely bonded to each other. According to this configuration, it is possible to further impart to the composition a cured property excellent in low dielectric properties which cannot be obtained by, for example, barium sulfate or a filler such as crushed or melted ceria.

The average particle diameter (D50) of the Novoloy bauxite particles is preferably 2.0 μm or less. The maximum particle diameter is preferably 5.0 μm or less. More preferably 3.0 μm or less.

The blending amount of the Novola alumina particles is preferably from 5 to 200 parts by mass, more preferably from 20 to 150 parts by mass, per 100 parts by mass of the carboxyl group-containing resin. When the blending amount of the Novola bauxite particles is within this range, the low dielectric constant of the cured product can be more reliably maintained, and the dispersion of the curable resin composition can be suppressed, and the thixotropy can be significantly improved. .

The Nobelic bauxite particles include Sillitin V85, Sillitin V88, Sillitin N82, Sillitin N85, Sillitin N87, Sillitin Z86, Sillitin Z89, Sillikolloid P87, Sillitin N85 Phyllis, Sillitin Z86 Phyllis, Sillitin Z89 Phyllis, Sillikolloid P87 Phyllis (Hoffmann- Made by mineral company). These may be used alone or in combination of two or more.

The Novo-Fork alumina particles can also be used as a surface treatment in order to obtain sufficient wettability to the resin. For example, the surface treatment may be carried out by an amino decane, a mercapto decane, or a vinyl decane, a methacryl decane, an epoxy decane, an alkyl decane or the like.

The Nobelic alumina particles subjected to the surface treatment may be exemplified by Aktisil VM56, Aktisil MAM, Aktisil MAM-R, Aktisil EM, Aktisil AM, Aktisil MM, Aktisil PF777 (manufactured by Hoffmann-mineral Co., Ltd.), or the like. These may be used alone or in combination of two or more.

The coloring agent can be formulated as a further additive component in the curable resin composition of the present invention. As the coloring agent, a conventionally known coloring agent such as red, blue, green, yellow, white or black may be used, and any of a pigment, a dye, and a coloring matter may be used. Specifically, it is listed as the color coefficient (C.I.; The Society of Dyers and Colourists) number. However, in terms of reducing environmental load and affecting the human body, it is preferred that halogen is not contained.

The blending ratio of the coloring agent is not particularly limited, but is preferably 5% by mass or less, preferably 0.1 to 3% by mass, based on the solid content of the composition. However, when it is a white curable resin composition, it is preferably from 1 to 50% by mass.

As the coloring agent used in the white curable resin composition, for example, rutile-type titanium oxide such as CR-50, CR-60 or CR-90 manufactured by Ishihara Sangyo Co., Ltd. is preferably used.

In the curable resin composition of the present invention, in addition to the physical strength of the coating film, a filler other than the perovskite compound or the Novoloy alumina particles may be blended as another additive component. As the filler, conventionally used inorganic or organic fillers can be used, and in particular, barium sulfate, spherical cerium oxide, and talc, clay, kaolin, hydrotalcite, and the like can be preferably used. Further, in order to obtain flame retardancy, a metal hydroxide such as a metal oxide or aluminum hydroxide may be used as the extender pigment filler. The blending amount of the filler is preferably 75% by mass or less, more preferably 0.1 to 60% by mass based on the total amount of the composition. When the amount of the filler is within this range, the coating and the moldability are more excellent, and a good cured product is obtained.

Further, in the curable resin composition of the present invention, an organic solvent can be used as the other additive component in order to adjust the viscosity when applied to the substrate or the carrier film.

The organic solvent may, for example, be a ketone, an aromatic hydrocarbon, a glycol ether, a glycol ether acetate, an ester, an alcohol, an aliphatic hydrocarbon or a petroleum solvent. More specifically, it is a ketone such as methyl ethyl ketone or cyclohexanone; an aromatic hydrocarbon such as toluene, xylene or tetramethylbenzene; fibrin, methyl cellosolve, butyl cellosolve, Glycol ethers such as carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether, etc.; ethyl acetate, acetic acid Esters such as butyl ester, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol diethyl ether acetate, propylene glycol butyl ether acetate, methyl 2-hydroxyisobutyrate; ethanol, propanol, ethylene Alcohols such as alcohols and propylene glycol; aliphatic hydrocarbons such as octane and decane; petroleum solvents such as petroleum ether, petroleum brain, hydrogenated petroleum brain, and solvent petroleum brain. These organic solvents may be used singly or in combination of two or more.

The curable resin composition of the present invention may further contain a conventionally known tackifier, a fine powder of cerium oxide, an organic bentonite, a montmorillonite, a conventionally used tackifier, an anthrone, a fluorine system, or a polymer system. Wait Conventional additives such as antifoaming agents and/or leveling agents, decane coupling agents, antioxidants, ultraviolet absorbers, and rust inhibitors.

The curable resin composition of the present invention as described above is used for the production of a printed circuit board by, for example, the following method.

First, the curable resin composition of the present invention is adjusted to a viscosity suitable for a coating method by, for example, the above-described organic solvent, and is subjected to a dip coating method, a flow coating method, a roll coating method, a bar coating method, or a screen printing method. A method such as a printing method or a curtain flow coating method is applied to a substrate, and the organic solvent contained in the composition is volatilized and dried (temporarily dried) at a temperature of about 60 to 100 ° C to form a non-tacky coating film.

Here, as the above-mentioned substrate, in addition to a printed circuit board or a flexible printed circuit board in which a circuit is formed in advance, paper-phenol resin, paper-epoxy resin, glass cloth-epoxy resin, glass-polyamide may be used. Amine, glass cloth / non-woven fabric - epoxy resin, glass cloth / paper - epoxy resin, synthetic fiber - epoxy resin, fluororesin. Polyethylene. PPO. A copper-clad laminate, a polyimide film, a PET film, a glass substrate, a ceramic substrate, a wafer plate, or the like of all grades (FR-4, etc.) of a composite material such as a cyanate ester.

Further, the curable resin composition of the present invention may be subjected to volatilization and drying after application, and a hot air circulating type drying furnace, an IR furnace, a hot plate, a ventilating oven, or the like (drying using a heat source having an air heating method by steam) may be used. The hot air convection contact method in the machine and the manner in which the support is blown by the nozzle are performed.

Next, the dry coating film formed on the substrate is contact-type (or non-contact) through the photomask forming the pattern by selective irradiation activity Exposure to the energy line, or direct exposure to the laser direct exposure machine. Thereby, the exposed portion (the portion irradiated with the active energy ray) of the dried coating film is hardened.

Here, as the exposure machine for the active energy ray irradiation, an exposure machine equipped with a metal halide lamp, an exposure machine equipped with a (super) high pressure mercury lamp, an exposure machine equipped with a mercury short arc lamp, or an (ultra) high voltage can be used. A direct drawing device for an ultraviolet lamp such as a mercury lamp, for example, a laser direct image forming device that directly draws an image using laser data from a computer. Further, although the exposure amount varies depending on the film thickness or the like, it is usually in the range of 5 to 800 mJ/cm ² , preferably 5 to 500 mJ/cm ² . In particular, as the direct drawing device, for example, a product manufactured by ORBETECH Co., Ltd., PENTAX Corporation, or the like can be used. Any device that can oscillate laser light having a maximum wavelength of 350 to 410 nm can be used as a gas laser or a solid thunder. Shoot.

Further, the unexposed portion may be developed by an aqueous alkali solution (for example, a 0.3 to 3 wt% aqueous sodium carbonate solution) to form a patterned insulating layer on the substrate.

Here, the development method may be carried out by dipping, rinsing, spraying, brushing, etc., using potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium citrate, ammonia, amines. The alkaline aqueous solution is treated as a developing solution.

Then, by heat-hardening to a temperature of, for example, about 140 to 180 ° C, a solder resist having excellent properties such as heat resistance, chemical resistance, moisture absorption resistance, adhesion, and electrical properties can be formed on the substrate. Hardening coating membrane.

The curable resin composition of the present invention may be applied to a film such as polyethylene terephthalate in advance, in addition to the method of directly applying the liquid to the substrate as described above, and dried by drying. The form of the dry film of the coating film is used. The case where the curable resin composition of the present invention is used as a dry film is shown below.

The dry film is a structure having a sequential build-up carrier film, a curable resin composition layer, and a peelable protective film as needed. The curable resin composition layer is, for example, a layer obtained by applying a photo-developable photocurable thermosetting resin composition to a carrier film or a protective film and drying it. After the curable resin composition layer is formed on the carrier film, a protective film is laminated thereon, or a curable resin composition layer is formed on the protective film, and a dry film is obtained by laminating the laminate on the carrier film.

As the carrier film, a thermoplastic film such as a polyethylene terephthalate film having a thickness of 2 to 150 μm is used.

The curable resin composition layer is uniformly applied to the carrier in a thickness of 10 to 150 μm by a doctor blade coater, a lip coater, a notch coater, a film coater or the like. The film or protective film is formed by drying.

A polyethylene film, a polypropylene film, or the like can be used as the protective film, but the adhesive force with the curable resin composition may be smaller than that of the carrier film.

When a permanent protective film (solder resist) is formed on a printed circuit board by using the dry film, the protective film is peeled off, and the curable resin composition layer and the substrate on which the circuit is formed are bonded together by a laminator or the like to form a film. Electricity A layer of a curable resin composition is formed on the substrate of the road. When the formed curable resin composition layer is subjected to exposure, development, and heat curing in the same manner as in the case of the above liquid composition, a cured coating film can be formed. Further, the carrier film may be peeled off before any of exposure or after exposure.

[Examples]

The invention is specifically illustrated by the following examples and comparative examples, but the invention is not limited by the following examples. In addition, the following "parts" and "%" are all based on quality unless otherwise specified.

<Synthesis example of carboxyl group-containing resin>

(Synthesis Example 1)

In the autoclave equipped with a thermometer, a nitrogen gas introducing device, an alkylene oxide introducing device, and a stirring device, a novolac type cresol resin (manufactured by Showa Polymer Co., Ltd., trade name "SHONOL CRG951", OH equivalent: 119.4) was fed. 119.4 parts, 1.19 parts of potassium hydroxide and 119.4 parts of toluene, the system was replaced with nitrogen while stirring, and heated to heat. Subsequently, 63.8 parts of propylene oxide was slowly added dropwise, and the mixture was reacted at 125 to 132 ° C for 0 to 4.8 kg/cm ² for 16 hours. Subsequently, it was cooled to room temperature, and 1.56 parts of 89% phosphoric acid was added to the reaction solution to neutralize potassium hydroxide to obtain a propylene oxide of a novolac type cresol resin having a nonvolatile content of 62.1% and a hydroxyl value of 182.2 g/eq. Reaction solution. It is an average of 1.08 moles of alkoxylated gas per phenol equivalent of a phenolic hydroxyl group.

Next, the obtained alkylene oxide reaction solution of the novolac type cresol resin 293.0 parts, 43.2 parts of acrylic acid, 11.53 parts of methanesulfonic acid, 0.18 parts of methylhydroquinone, and 252.9 parts of toluene were fed into a reactor equipped with a stirrer, a thermometer, and an air blowing tube, and air was blown at a rate of 10 ml/min while stirring. The reaction was carried out at 110 ° C for 12 hours. The water produced by the reaction was distilled off in an azeotropic mixture with toluene to 12.6 parts of water. Subsequently, it was cooled to room temperature, and the resulting reaction solution was neutralized with 35.35 parts of a 15% aqueous sodium hydroxide solution, followed by washing with water. Subsequently, the toluene was distilled off with 118.1 parts of diethylene glycol monoethyl ether acetate as an evaporator to obtain a novolac type acrylate resin solution. Next, 332.5 parts of the obtained novolac type acrylate resin solution and 1.22 parts of triphenylphosphine were fed into a reactor equipped with a stirrer, a thermometer, and an air blowing tube, and air was blown at a rate of 10 ml/min, and stirred while stirring. 60.8 parts of tetrahydrophthalic anhydride was slowly added, and the reaction was carried out at 95 to 101 ° C for 6 hours. A resin solution of a photosensitive resin containing a carboxyl group having a solid content of 88 mg KOH/g, a nonvolatile content of 71%, and a Mw of about 10,000 was obtained. Hereinafter, the resin solution is referred to as A-1.

(Synthesis Example 2)

Methanol methacrylate, ethyl methacrylate and methacrylic acid in a molar ratio of 1:1:2 were fed into a flask equipped with a thermometer, a stirrer, a dropping funnel and a reflux condenser, and added as a solvent. Dipropylene glycol monomethyl ether and azobisisobutyronitrile (AIBN) as a catalyst were stirred at 80 ° C for 4 hours under a nitrogen atmosphere to obtain a resin solution. The resin solution was cooled, and the above resin was used at a temperature of 95 to 105 ° C for 16 hours using methylhydroquinone as a polymerization inhibitor and tetrabutylphosphonium bromide as a catalyst. The carboxyl group addition reaction 20 mol% of glycidyl methacrylate was taken out after cooling. The carboxyl group-containing photosensitive resin having an ethylenically unsaturated bond and a carboxyl group thus obtained had a solid content of an acid value of 120 mgKOH/g, a nonvolatile content of 71%, and a Mw of about 20,000. This resin solution is referred to as A-2.

(Examples 1 to 12, Comparative Examples 1 to 3)

Each component shown in the following Table 1 was kneaded by a 3-axis roller, and the resin compositions of Examples 1 to 12 and Comparative Examples 1 to 3 were obtained. The numbers in the table indicate the parts by mass.

*1 Melamine: manufactured by Nissan Chemical Industries Co., Ltd. *2 JER Cure DICY7: manufactured by Mitsubishi Chemical Corporation *3 CI Pigment Blue 15:3*4 CI Pigment Yellow 147*5 TIPAQUE CR90: Ishihara Industry Co., Ltd.*6 LUCIRIN TPO: Japan BASF Corporation Manufacture ※7 KAYACURE DETX-S: manufactured by Nippon Kayaku Co., Ltd. ※8 Irgacure OXE02: manufactured by BASF, Japan ※9 RE-306: manufactured by Nippon Kayaku Co., Ltd. ※10 YX-4000: manufactured by Mitsubishi Chemical Corporation ※11 DPHA: Nippon Chemical Manufactured by the company ※12 Laromer LR8868 (3-functional acrylate monomer): manufactured by BASF, Japan ※13 Dipropylene glycol monomethyl ether ※14 Aktisil EM: manufactured by HOFFMANN MINERAL Sillitin*15 B-30: 表面Chemical Industries, Inc. *16 CT-30 (calcium titanate): manufactured by 堺Chemical Industries Co., Ltd. ※17 ST-03 (barium titanate): 堺Chemical Industry Co., Ltd. ※18 CZ-03 (calcium zirconate): 堺Chemical Industry Co., Ltd. ※19 CT-03 (锶 锆 锶): manufactured by 堺Chemical Industries Co., Ltd. ※20 BT-03 (barium titanate): manufactured by 堺Chemical Industries

<Test of solder heat resistance and pencil hardness>

(Evaluation of substrate production)

The compositions obtained in the above Examples 1 to 12 and Comparative Examples 1 to 3 were applied by screen printing to a copper foil substrate having a pattern, dried at 80 ° C for 30 minutes, and allowed to cool to room temperature. This substrate was exposed to a pattern using an exposure apparatus equipped with a high-pressure mercury lamp, and exposed to a pattern of an optimum amount of exposure, and developed with a sodium carbonate aqueous solution of 30° C. at a pressure of 0.2 MPa at a pressure of 0.2 MPa to obtain a pattern. The solder resist layer. The substrate was irradiated with ultraviolet rays under the conditions of a cumulative exposure amount of 1000 mJ/cm ² by a UV transfer furnace, and then cured by heating at 160 ° C for 60 minutes. The evaluation substrate was produced in this manner.

Here, the optimum exposure amount means the following exposure amount. That is, a circuit pattern substrate having a copper thickness of 18 μm is subjected to roughening treatment on a copper surface (Merck Etch Bond CZ-8100 manufactured by Merck), washed with water, dried, and coated with the above-described embodiment by screen printing. And the curable resin composition of the comparative example was dried in a hot air circulating drying oven at 80 ° C for 30 minutes, dried, and exposed by a stepping apparatus (Kodak No. 2) using an exposure apparatus equipped with a high pressure mercury lamp, and The pattern of the step change pattern remaining when the image was developed for 90 seconds (30 ° C, 0.2 MPa, 1% by mass aqueous sodium carbonate solution) was the exposure amount at the 7th step.

The evaluation substrate thus obtained was evaluated for solder heat resistance and pencil hardness as follows.

(solder heat resistance)

The evaluation substrate coated with the rosin flux was immersed in a solder bath set at 260 ° C in advance, and the flux was washed with modified alcohol to visually observe the expansion of the resist layer. Stripped and evaluated.

The evaluation criteria are as follows.

○: Peeling was not confirmed even after repeated immersion for 10 seconds or more.

△: There was a slight peeling when the immersion was repeated for 10 seconds or more.

×: After immersing for 10 times or less, the resist layer was swollen and peeled off.

(pencil hardness)

The cured coating film of the substrate was evaluated in accordance with the test method of JIS K 5600, and the highest hardness of the coating film was not damaged.

<Evaluation of insulation resistance>

(Evaluation of substrate production)

According to the method for producing the above-mentioned evaluation substrate, the compositions obtained in the above Examples 1 to 12 and Comparative Examples 1 to 3 were applied onto a copper foil substrate on which an IPC comb-type B pattern was formed, and cured to prepare an evaluation substrate.

(evaluation method)

The evaluation substrate thus prepared was measured for the absolute impedance value of the 1-point value at DC 500 V, and was evaluated as an initial value. Further, the insulation resistance value of 1 point of the insulation resistance after 168 hours of humidification at 90% RH, 25 to 65 ° C, and DC 100 V was measured by DC 500 V.

<Evaluation of dielectric constant and dielectric tangent>

(production of test piece)

The compositions obtained in the above Examples 1 to 12 and Comparative Examples 1 to 3 were each appropriately diluted with methyl ethyl ketone, and then applied to a PET film by using a cloth coater so that the film thickness after drying was 20 μm (TORAY Corporation) Manufactured on FB-50: 16 μm), dried at 80 ° C for 30 minutes to obtain a dry film. Using a vacuum laminator (manufactured by Nago Seisakusho Co., Ltd., MVLP (registered trademark)-500), the obtained dry film was heated and laminated under the conditions of a pressure of 0.8 MPa, 70 ° C, 1 minute, and a degree of vacuum of 133.3 Pa. On an electrolytic copper foil (manufactured by Furukawa Electric Co., Ltd.) having a thickness of 9 μm. The dry film laminated on the copper foil was exposed to an optimum exposure amount using an exposure apparatus equipped with a high-pressure mercury lamp (short arc lamp), and the PET film was peeled off. After the dry film is thermally laminated on the exposed dry film again, it is fully exposed at an optimum exposure amount. A dry film layer having a thickness of 400 μm was formed on the copper foil by repeating the lamination and exposure 20 times. The copper foil thus formed into a dry film layer was irradiated with ultraviolet rays under a condition of an accumulated exposure amount of 1000 mJ/cm ² in a UV transfer furnace, and then heated at 160 ° C for 60 minutes to harden the dry film layer. Next, the copper foil with the dry film layer was etched and removed using an etching solution having a composition of 340 g/l of copper chloride and 51.3 g/l of a free hydrochloric acid, and sufficiently washed with water and dried to prepare a cured film having a thickness of 400 μm. The test piece made.

(evaluation method)

The dielectric constant and dielectric tangent of the thus-prepared test piece were measured at 1 GHz using an RF impedance/material analyzer (Agilent E4991A, manufactured by Agilent Technologies, Inc.). The evaluation criteria are as follows.

(dielectric rate)

○: The dielectric ratio is less than 4.

×: The dielectric constant is 4 or more.

(dielectric tangent)

○: The dielectric tangent was less than 0.01.

△: The dielectric tangent is 0.01 or more and less than 0.02.

×: Dielectric tangent exceeds 0.02.

As described above, the results of evaluation of solder heat resistance, pencil hardness, insulation resistance, dielectric constant, and dielectric tangent are shown in Table 1 above. As is apparent from the results shown in Table 1, according to the present embodiment, properties such as coating film hardness and solder heat stability were not deteriorated, and the cured product was low dielectric constant and low dielectric tangent, and showed stable insulation resistance.

Claims (5)

A curable resin composition characterized by containing a carboxyl group-containing resin and a composite oxide composed of calcium titanate, barium titanate, barium zirconate, calcium zirconate, barium zirconate, and the like as a main component At least one of the perovskite-type compounds. The curable resin composition of claim 1, further comprising at least one selected from the group consisting of a photocurable component and a thermosetting component. A dry film obtained by coating a film of the curable resin composition of claim 1 or claim 2 and drying it. A cured product obtained by hardening a curable resin composition of claim 1 or claim 2 or a dry film of claim 3. A printed circuit board characterized by having a hardened film obtained by hardening a curable resin composition as claimed in claim 1 or claim 2 or a dry film as claimed in claim 3.