JP2017522580A - Photocurable thermosetting resin composition for manufacturing printed wiring board, dry film, cured product, and printed wiring board - Google Patents

Abstract

The present invention comprises (A) a carboxyl group-containing resin, (B) a photopolymerization initiator, (C) a photosensitive monomer, (D) a thermosetting component, and (E) a hollow filler. A photocurable thermosetting resin composition for producing a printed wiring board, a dry film, a cured product, and a printed wiring board are provided. [Selection figure] None

Description

  The present invention relates to a photocurable thermosetting resin composition for production of a printed wiring board soluble in a dilute alkaline aqueous solution, a dry film and a cured product thereof, and a printed wiring board having a cured product formed using them. .

  Currently, photocurable thermosetting resin compositions for solder resists on some consumer printed wiring boards and most industrial printed wiring boards are developed after UV irradiation from the viewpoint of high accuracy and high density. A photo-curable thermosetting resin composition for a liquid development type solder resist that forms an image by the above and is finish-cured (mainly cured) by heat and / or light irradiation is used. Among them, in consideration of environmental problems, photocurable thermosetting resin compositions for photo-developing photo solder resists that use a dilute aqueous alkali solution as the developer are the mainstream, and the actual production of printed wiring boards. In large quantities.

JP 2013-539072 A

  One purpose of using a solder resist is to protect a printed wiring board as an insulating material. However, due to the recent high density mounting and large current of printed wiring boards, there is a problem that the solder resist behaves like a capacitor. When the solder resist behaves as a capacitor, a current that should not flow originally flows, causing a failure or malfunction of the electronic device. In order to solve this problem, it is necessary to lower the dielectric constant of the solder resist.

  An object of the present invention is to provide a photocurable thermosetting resin composition for manufacturing a printed wiring board capable of excellent reduction in dielectric constant, a dry film, a cured product thereof, and a printed wiring board having the cured product. It is in.

  The present inventors have intensively studied and succeeded in lowering the dielectric constant of a photocurable thermosetting resin composition for producing a printed wiring board, thereby completing the present invention.

  That is, according to the present invention, it contains (A) a carboxyl group-containing resin, (B) a photopolymerization initiator, (C) a photosensitive monomer, (D) a thermosetting component, and (E) a hollow filler. A photocurable thermosetting resin composition for producing a printed wiring board is provided. Here, in this invention, it is preferable that the average particle diameter d50 of the said (E) hollow filler is the range of 1 micrometer-100 micrometers. In the present invention, the (E) hollow filler is preferably hollow glass or hollow silica.

  According to this invention, the dry film for manufacture of the printed wiring board obtained by apply | coating to the carrier film and drying the photocurable thermosetting resin composition for manufacture of the said printed wiring board is provided.

  According to this invention, the hardened | cured material obtained by photocuring and thermosetting the photocurable thermosetting resin composition for manufacture of the said printed wiring board or the dry film for manufacture of the said printed wiring board is provided.

  According to this invention, the printed wiring board which has the said hardened | cured material is provided.

According to the present invention, by including a hollow filler, a photocurable thermosetting resin composition for producing a printed wiring board capable of achieving a low dielectric constant and a dry film for producing a printed wiring board are provided. can do.
Moreover, according to this invention, the hardened | cured material with a low dielectric constant and the printed wiring board which has the hardened | cured material can be provided.

  The present invention comprises a print comprising (A) a carboxyl group-containing resin, (B) a photopolymerization initiator, (C) a photosensitive monomer, (D) a thermosetting component, and (E) a hollow filler. It is a photocurable thermosetting resin composition for manufacturing a wiring board (hereinafter referred to as a photocurable thermosetting resin composition). Since the photocurable thermosetting resin composition of the present invention contains the components (A) to (E), a cured product having high sensitivity, low dielectric constant, and excellent solder heat resistance can be obtained. In the case of high sensitivity, the exposure time when obtaining a cured product can be shortened, leading to a reduction in tact time.

The (A) carboxyl group-containing resin in the photocurable thermosetting resin composition of the present embodiment is used for imparting alkali developability, and a known resin containing a carboxyl group in the molecule may be used. it can. In particular, from the viewpoint of photocurability and development resistance, a carboxyl group-containing resin having an ethylenically unsaturated double bond in the molecule is preferable. The unsaturated double bond is more preferably derived from acrylic acid, methacrylic acid or derivatives thereof.
(A) As carboxyl group-containing resin, carboxyl group-containing resin using epoxy resin as a starting material, carboxyl group-containing urethane resin having urethane skeleton, carboxyl group-containing copolymer resin having copolymer structure of unsaturated carboxylic acid, phenol A carboxyl group-containing resin starting from a compound is preferred.
Specific examples of the (A) carboxyl group-containing resin are shown below.

(1) A carboxyl group-containing resin obtained by copolymerization of an unsaturated carboxylic acid such as (meth) acrylic acid and an unsaturated group-containing compound such as styrene, α-methylstyrene, lower alkyl (meth) acrylate, and isobutylene.
(2) Diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, and aromatic diisocyanates, carboxyl group-containing dialcohol compounds such as dimethylolpropionic acid and dimethylolbutanoic acid, polycarbonate polyols, and polyethers A carboxyl group-containing urethane resin by a polyaddition reaction of a diol compound such as a polyol, a polyester polyol, a polyolefin polyol, an acrylic polyol, a bisphenol A alkylene oxide adduct diol, a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group.
(3) Diisocyanate compounds such as aliphatic diisocyanate, branched aliphatic diisocyanate, alicyclic diisocyanate, aromatic diisocyanate, polycarbonate polyol, polyether polyol, polyester polyol, polyolefin polyol, acrylic polyol, bisphenol A type A terminal carboxyl group-containing urethane resin obtained by reacting an acid anhydride with a terminal of a urethane resin by a polyaddition reaction of a diol compound such as an alkylene oxide adduct diol, a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group.
(4) Diisocyanate and bifunctional epoxy resin such as bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bixylenol type epoxy resin, biphenol type epoxy resin ( A carboxyl group-containing photosensitive urethane resin obtained by polyaddition reaction of (meth) acrylate or a partially acid anhydride modified product thereof, a carboxyl group-containing dialcohol compound, and a diol compound.
(5) During the synthesis of the resin described in (2) or (4) above, a compound having one hydroxyl group and one or more (meth) acryloyl groups in a molecule such as hydroxyalkyl (meth) acrylate is added, (Meth) acrylic carboxyl group-containing urethane resin.
(6) During the synthesis of the resin of (2) or (4) described above, one isocyanate group and one or more (meth) acryloyl groups in the molecule, such as an equimolar reaction product of isophorone diisocyanate and pentaerythritol triacrylate The carboxyl group-containing urethane resin which added the compound which has and was terminally (meth) acrylated.
(7) (meth) acrylic acid is reacted with a bifunctional or higher polyfunctional epoxy resin as described later, and the hydroxyl groups present in the side chain are added to 2 such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, etc. A carboxyl group-containing photosensitive resin to which a basic acid anhydride is added. Here, the epoxy resin is preferably solid.
(8) (meth) acrylic acid was reacted with a polyfunctional epoxy resin obtained by epoxidizing a hydroxyl group of a bifunctional epoxy resin as described later with epichlorohydrin, and a dibasic acid anhydride was added to the resulting hydroxyl group. Carboxyl group-containing photosensitive resin. Here, the epoxy resin is preferably solid.
(9) Cyclic ethers such as ethylene oxide or cyclic carbonates such as propylene carbonate are added to polyfunctional phenol compounds such as novolak, and the resulting hydroxyl groups are partially esterified with (meth) acrylic acid, and the remaining hydroxyl groups are A carboxyl group-containing photosensitive resin obtained by reacting a basic acid anhydride.
(10) In addition to these resins (1) to (9), one epoxy group and one or more (meth) acryloyl groups are added in the molecule such as glycidyl (meth) acrylate and α-methylglycidyl (meth) acrylate. A carboxyl group-containing photosensitive resin obtained by adding a compound having the same.

(A) The carboxyl group-containing resin can be used without being limited to these, and can be used by mixing one kind or plural kinds.
Here, (meth) acrylate is a generic term for acrylate, methacrylate, and mixtures thereof, and the same applies to other similar expressions.
(A) Since the carboxyl group-containing resin has a number of free carboxyl groups in the side chain of the backbone polymer, development with a dilute aqueous alkali solution is possible.

  (A) The acid value of the carboxyl group-containing resin is preferably 40 to 200 mgKOH / g. (A) When the acid value of the carboxyl group-containing resin is 40 mgKOH / g to 200 mgKOH / g or less, adhesion of the cured film is obtained, alkali development is facilitated, and dissolution of the exposed portion by the developer is suppressed, which is necessary. A normal resist pattern can be easily drawn without fading the lines. More preferably, it is 45-120 mgKOH / g.

  (A) The weight average molecular weight of the carboxyl group-containing resin varies depending on the resin skeleton, but is generally preferably 2,000 to 150,000. When it is in the range of 2,000 to 150,000, the tack-free performance is good, the moisture resistance of the cured film after exposure is good, and film loss is unlikely to occur during development. Further, when the weight average molecular weight is within the above range, the resolution is improved, the developability is good, and the storage stability is improved. More preferably, it is 5,000-100,000.

  (A) 20-80 mass% is suitable for the compounding quantity of carboxyl group-containing resin in a photocurable thermosetting resin composition. When it is 20% by mass or more and 80% by mass or less, the film strength is good, the viscosity of the composition can be lowered, and the coating property and the like are excellent. More preferably, it is 30-60 mass%.

  As the photopolymerization initiator (B) that can be suitably used for the photocurable thermosetting resin composition of the present invention, an oxime ester photopolymerization initiator having an oxime ester group, an alkylphenone photopolymerization initiator, One or more photopolymerization initiators selected from the group consisting of α-aminoacetophenone photopolymerization initiators, acylphosphine oxide photopolymerization initiators, and titanocene photopolymerization initiators can be suitably used.

  Examples of the oxime ester photopolymerization initiator include CGI-325, Irgacure OXE01, Irgacure OXE02 manufactured by BASF Japan, N-1919, NCI-831 manufactured by Adeka, and the like as commercially available products. Moreover, the photoinitiator which has two oxime ester groups in a molecule | numerator can also be used suitably. As the oxime ester photopolymerization initiator, an oxime ester compound having a carbazole structure is preferable.

  Examples of commercially available alkylphenone photopolymerization initiators include α-hydroxyalkylphenone types such as Irgacure 184, Darocur 1173, Irgacure 2959, and Irgacure 127 manufactured by BASF Japan.

  As the α-aminoacetophenone photopolymerization initiator, specifically, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, N , N-dimethylaminoacetophenone and the like. Examples of commercially available products include Irgacure 907, Irgacure 369, and Irgacure 379 manufactured by BASF Japan.

Specific examples of the acylphosphine oxide photopolymerization initiator include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and bis (2,6-dimethoxy). And benzoyl) -2,4,4-trimethyl-pentylphosphine oxide. Examples of commercially available products include Lucilin TPO manufactured by BASF, Irgacure 819 manufactured by BASF Japan, and the like.
In addition, titanocene photopolymerization initiators such as Irgacure 389 and Irgacure 784 manufactured by BASF Japan can also be suitably used as the photopolymerization initiator.

  (B) The blending amount of the photopolymerization initiator is preferably 0.1 to 25 parts by mass and more preferably 1 to 20 parts by mass with respect to 100 parts by mass of the (A) carboxyl group-containing resin. . By being 0.1 to 25 parts by mass, a cured film having excellent photocurability and resolution, improved adhesion and PCT resistance, and excellent chemical resistance such as electroless gold plating resistance is obtained. be able to. In particular, when it is 25 parts by mass or less, an effect of reducing outgas can be obtained, and further, light absorption at the surface of the cured coating becomes intense, and it is possible to suppress a decrease in deep part curability.

  The said photocurable thermosetting resin composition can use a photoinitiator adjuvant and a sensitizer other than a photoinitiator. Examples of the photopolymerization initiator, photoinitiator assistant, and sensitizer that can be suitably used for the photocurable thermosetting resin composition include benzoin compounds, acetophenone compounds, anthraquinone compounds, thioxanthone compounds, ketal compounds, benzophenone compounds, A tertiary amine compound, a xanthone compound, etc. can be mentioned.

  These photopolymerization initiators, photoinitiator assistants, and sensitizers can be used alone or as a mixture of two or more. The total amount of such photopolymerization initiator, photoinitiator assistant, and sensitizer is preferably 35 parts by mass or less with respect to 100 parts by mass of (A) carboxyl group-containing resin. It can suppress that deep part curability falls by these light absorption as it is 35 mass parts or less.

  (C) As a photosensitive monomer, a compound having two or more ethylenically unsaturated groups in a molecule, a compound obtained by adding an α, β-unsaturated carboxylic acid to a polyhydric alcohol, a glycidyl group-containing compound A compound obtained by adding an α, β-unsaturated carboxylic acid is used.

  Examples of the compound having two or more ethylenically unsaturated groups in the molecule include diacrylates of glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol; hexanediol, trimethylolpropane, and pentaerythritol. , Polyhydric alcohols such as dipentaerythritol, tris-hydroxyethyl isocyanurate or the like, or polyethyl acrylates such as ethylene oxide adduct or propylene oxide adduct; phenoxy acrylate, bisphenol A diacrylate, and ethylene of these phenols Multivalent acrylates such as oxide adducts or propylene oxide adducts; glycerin diglycidyl ether, glycerin triglycidyl ether Trimethylolpropane triglycidyl ether, polyvalent acrylates of glycidyl ethers such as triglycidyl isocyanurate; and melamine acrylate, and / or each methacrylates corresponding to the above acrylate.

  Examples of the compound obtained by adding an α, β-unsaturated carboxylic acid to a polyhydric alcohol include, for example, ethylene glycol diacrylate, diethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, propylene glycol diacrylate, and polypropylene. Glycol diacrylate, butylene glycol diacrylate, pentyl glycol diacrylate, 1,6-hexanediol diacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, tetramethylolmethane triacrylate, tetramethylolmethane tetraacrylate, glycerin diacrylate , Pentaerythritol diacrylate, pentaerythritol triacrylate , Dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and / or each methacrylate corresponding to the above acrylate.

  Examples of the compound obtained by adding an α, β-unsaturated carboxylic acid to a glycidyl group-containing compound include ethylene glycol diglycidyl ether diacrylate, diethylene glycol diglycidyl ether diacrylate, trimethylolpropane triglycidyl ether triacrylate, and bisphenol. A glycidyl ether diacrylate, phthalic acid diglycidyl ester diacrylate, glycerin polyglycidyl ether polyacrylate, etc .; 2,2-bis (4-acryloyloxydiethoxyphenyl) propane, 2,2-bis- (4-acryloyl) Oxypolyethoxyphenyl) propane, 2-hydroxy-3-acryloyloxypropyl acrylate, and / or methacrylates corresponding to the acrylate Etc. These photosensitive monomers can be used individually or in combination of multiple types.

  (C) As for the compounding quantity of the photosensitive monomer, 5-100 mass parts is preferable with respect to 100 mass parts of (A) carboxyl group-containing resin, More preferably, it is 10-90 mass parts, More preferably, 15 mass parts- It is preferably 85 parts by mass. By setting it as the range of the said compounding quantity, photocurability improves, pattern formation becomes easy and the intensity | strength of a cured film can also be improved.

  (D) Known thermosetting components such as blocked isocyanate compounds, amino resins, maleimide compounds, benzoxazine resins, carbodiimide resins, cyclocarbonate compounds, polyfunctional epoxy compounds, polyfunctional oxetane compounds, episulfide resins, melamine derivatives, etc. The thermosetting resin can be used. Among these, a preferable thermosetting component is a thermosetting component having two or more cyclic ether groups and / or cyclic thioether groups (hereinafter abbreviated as cyclic (thio) ether groups) in one molecule. There are many commercially available thermosetting components having a cyclic (thio) ether group, and various properties can be imparted depending on the structure.

  Such a thermosetting component having two or more cyclic (thio) ether groups in the molecule is either one of the three-, four- or five-membered cyclic ether groups in the molecule, or the cyclic thioether group, or two of them. A compound having at least two epoxy groups in the molecule, for example, a polyfunctional epoxy compound (D-1) having at least two oxetanyl groups in the molecule. Examples thereof include a compound, that is, a polyfunctional oxetane compound (D-2), a compound having two or more thioether groups in the molecule, that is, an episulfide resin (D-3).

  Examples of the polyfunctional epoxy compound (D-1) include jER828, jER834, jER1001, and jER1004 manufactured by Japan Epoxy Resin, Epicron 840, Epicron 850, Epicron 1050, Epicron 1050, and Epitome 2055 manufactured by Dainippon Ink & Chemicals, Inc. Epototo YD-011, YD-013, YD-127, YD-128 manufactured by Kasei Co., Ltd., D.C. E. R. 317, D.E. E. R. 331, D.D. E. R. 661, D.D. E. R. 664, Ciba Specialty Chemicals' Araldide 6071, Araldide 6084, Araldide DY250, Araldide DY260, Sumitomo Chemical Industries Sumi-Epoxy ESA-011, ESA-014, ELA-115, ELA-128, Asahi Kasei Kogyo Co., Ltd. A. E. R. 330, A.I. E. R. 331, A.I. E. R. 661, A.I. E. R. 664 etc. (all trade names) bisphenol A type epoxy resin; jERYL903 manufactured by Japan Epoxy Resin, Epicron 152, Epicron 165 manufactured by Dainippon Ink and Chemicals, Epototo YDB-400, YDB-500 manufactured by Tohto Kasei Co., Ltd. D. Chemicals manufactured by Dow Chemical Company. E. R. 542, Araldide 8011 manufactured by Ciba Specialty Chemicals, Sumi-epoxy ESB-400, ESB-700 manufactured by Sumitomo Chemical Co., Ltd., and A.D. E. R. 711, A.I. E. R. 714 (both trade names) brominated epoxy resin; jER152, jER154 manufactured by Japan Epoxy Resin, D.C. E. N. 431, D.D. E. N. 438, Epicron N-730, Epicron N-770, Epicron N-865, Etototo YDCN-701, YDCN-704 from Toto Kasei Co., Ltd., Araldide ECN1235 from Ciba Specialty Chemicals, Araldide ECN1273, Araldide ECN1299, Araldide XPY307, Nippon Kayaku Co., Ltd. EPPN-201, EOCN-1025, EOCN-1020, EOCN-104S, RE-306, Sumitomo Chemical Industries Sumi-epoxy ESCN-195X, ESCN- 220, manufactured by Asahi Kasei Corporation. E. R. Novolak type epoxy resins such as ECN-235, ECN-299, etc. (both trade names); Epicron 830 manufactured by Dainippon Ink and Chemicals, jER807 manufactured by Japan Epoxy Resin, Epototo YDF-170 manufactured by Toto Kasei Co., Ltd., YDF- 175, YDF-2004, Araldide XPY306 manufactured by Ciba Specialty Chemicals, etc. (both trade names); Epototo ST-2004, ST-2007, ST-3000 (trade names, manufactured by Toto Kasei) Hydrogenated bisphenol A type epoxy resin such as JER604 manufactured by Japan Epoxy Resin Co., Ltd., Epotot YH-434 manufactured by Toto Kasei Co., Ltd., Araldide MY720 manufactured by Ciba Specialty Chemicals Co., Ltd., Sumi-Epoxy ELM manufactured by Sumitomo Chemical Co., Ltd. -120 etc. (both Product name) Glycidylamine type epoxy resin; Ardandide type epoxy resin such as araldide CY-350 (trade name) made by Ciba Specialty Chemicals; Celoxide 2021 made by Daicel Chemical Industries, Araldide made by Ciba Specialty Chemicals CY175, CY179, etc. (both trade names); YL-933 manufactured by Japan Epoxy Resin Co., Ltd. E. N. , EPPN-501, EPPN-502, etc. (all trade names) trihydroxyphenylmethane type epoxy resin; Japan Epoxy Resin YL-6056, YX-4000, YL-6121 (all trade names), etc. Xylenol type or biphenol type epoxy resin or a mixture thereof; bisphenol S type such as EBPS-200 manufactured by Nippon Kayaku Co., Ltd., EPX-30 manufactured by Asahi Denka Kogyo Co., Ltd., EXA-1514 (trade name) manufactured by Dainippon Ink & Chemicals, Inc. Epoxy resin; bisphenol A novolak type epoxy resin such as jER157S (trade name) manufactured by Japan Epoxy Resin; jERYL-931 manufactured by Japan Epoxy Resin, Araldide 163 manufactured by Ciba Specialty Chemicals (all trade names) Tetraphenylolethane type epoxy Fats; heterocyclic epoxy resins such as Araldide PT810 manufactured by Ciba Specialty Chemicals, TEPIC manufactured by Nissan Chemical Industries, Ltd. (both trade names); diglycidyl phthalate resins such as Bremer DDT manufactured by Nippon Oil &Fats; Toto Kasei Co., Ltd. Tetraglycidylxylenoylethane resins such as ZX-1063 manufactured by Nippon Steel Chemical Co., Ltd .; Naphthalene groups such as ESN-190 and ESN-360 manufactured by Nippon Steel Chemical Co., Ltd., HP-4032, EXA-4750, EXA-4700 manufactured by Dainippon Ink and Chemicals, Inc. Containing epoxy resin; Epoxy resin having a dicyclopentadiene skeleton such as HP-7200, HP-7200H manufactured by Dainippon Ink &Chemicals; Glycidyl methacrylate copolymer epoxy resin such as CP-50S, CP-50M manufactured by Nippon Oil & Fats Co., Ltd. Cyclohexyl maleimide and glycidyl methacrylate Relate copolymerized epoxy resins; epoxy-modified polybutadiene rubber derivatives (for example, PB-3600 manufactured by Daicel Chemical Industries, Ltd.), CTBN-modified epoxy resins (for example, YR-102, YR-450 manufactured by Tohto Kasei Co., Ltd.) and the like. However, it is not limited to these. These epoxy resins can be used alone or in combination of two or more. Among these, novolak-type epoxy resins, modified novolak-type epoxy resins, heterocyclic epoxy resins, bixylenol-type epoxy resins or mixtures thereof are particularly preferable.

  Examples of the polyfunctional oxetane compound (D-2) include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [(3-ethyl-3-oxetanylmethoxy) methyl] ether, 1,4-bis [(3-Methyl-3-oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, (3-methyl-3-oxetanyl) methyl acrylate, (3- In addition to polyfunctional oxetanes such as ethyl-3-oxetanyl) methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate and oligomers or copolymers thereof, oxetane Alcohol and novolak resin, poly (p-hydroxystyrene), cardo type Scan phenols, calixarenes, calix resorcin arenes, or the like ethers of a resin having a hydroxyl group such as silsesquioxane and the like. In addition, a copolymer of an unsaturated monomer having an oxetane ring and an alkyl (meth) acrylate is also included.

  Examples of the episulfide resin (D-3) having two or more cyclic thioether groups in the molecule include YL7000 (bisphenol A type episulfide resin) manufactured by Japan Epoxy Resin Co., Ltd. and YSLV-120TE manufactured by Toto Kasei Co., Ltd. Etc. Moreover, episulfide resin etc. which replaced the oxygen atom of the epoxy group of the novolak-type epoxy resin with the sulfur atom using the same synthesis method can be used.

As for the compounding quantity of a thermosetting component, 10-100 mass parts is preferable with respect to 100 mass parts of (A) carboxyl group-containing resin.
In particular, the compounding amount of the thermosetting component having two or more cyclic (thio) ether groups in the molecule is such that the cyclic (thio) ether group is equivalent to 1 equivalent of the carboxyl group of the (A) carboxyl group-containing resin. The range is preferably 0.6 to 2.5 equivalents, more preferably 0.8 to 2.0 equivalents. When the blending amount of the thermosetting component is within the above range, the heat resistance, alkali resistance, electrical insulation, strength of the cured film, etc. are good.

(E) A hollow filler is a filler with a hollow inside. The average particle diameter d50 of the hollow filler is preferably 1 μm to 110 μm, more preferably 10 μm to 100 μm.
The hollow filler may be any as long as the inside is hollow, but is preferably hollow glass or hollow silica.
Specific examples of the hollow glass include Glass Bubbles K1, K15, K20, S22, K25, K37, S38, VS5500, S42XHS, K46, iM16K, S60J, S60HS, iM30K, Potters Barotini, manufactured by Sumitomo 3M Limited. Examples include Sphericel 110P8, 60P18, 34P30, 25P45, Q-CEL 5020, 5020FPS, 7014, 7040S, Ceramic Multi Cellular CMC-20, CMC-15L, and Extendosphere SG. Specific examples of the hollow silica include Julia Catalytic Chemical's Sululia 1110.
A hollow filler can be used 1 type or in combination of 2 or more types.

  (E) The compounding quantity of a hollow filler becomes like this. Preferably it is 200 mass parts or less with respect to 100 mass parts of (A) carboxyl group-containing resin, More preferably, it is 20-150 mass parts, Most preferably, it is 30-130 mass parts. is there. (E) The hardened | cured material with favorable printability and high intensity | strength is obtained as the compounding quantity of a hollow filler is 200 mass parts or less.

  Furthermore, the photocurable thermosetting resin composition of this invention can use (F) binder polymer for the purpose of the improvement of touch drying property, the improvement of handling property, etc. For example, polyester polymers, polyurethane polymers, polyester urethane polymers, polyamide polymers, polyester amide polymers, acrylic polymers, cellulose polymers, polylactic acid polymers, phenoxy polymers, and the like can be used. These binder polymers can be used alone or as a mixture of two or more.

  Furthermore, the photocurable thermosetting resin composition of the present invention can use other elastomers for the purpose of imparting flexibility and improving brittleness of the cured product. For example, a polyester elastomer, a polyurethane elastomer, a polyester urethane elastomer, a polyamide elastomer, a polyesteramide elastomer, an acrylic elastomer, or an olefin elastomer can be used. Moreover, the resin etc. which modified the one part or all part of the epoxy resin which has various frame | skeleton with the both-ends carboxylic acid modified butadiene-acrylonitrile rubber | gum can be used. Furthermore, epoxy-containing polybutadiene elastomers, acrylic-containing polybutadiene elastomers, and the like can also be used. These elastomers can be used alone or as a mixture of two or more.

Further, the photocurable thermosetting resin composition of the present invention is an organic solvent for (A) synthesis of a carboxyl group-containing resin, adjustment of the composition, or adjustment of viscosity for application to a substrate or carrier film. Can be used.
Examples of such organic solvents include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, petroleum solvents, and the like. More specifically, ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl Glycol ethers such as ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether; ethyl acetate, butyl acetate, diethylene glycol ethyl ether acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, Propylene glycol ethyl ether acetate, propylene glycol butyl ether acetate Esters such as carbonates; Alcohols such as ethanol, propanol, ethylene glycol, and propylene glycol; Aliphatic hydrocarbons such as octane and decane; Petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha It is. Such organic solvents are used alone or as a mixture of two or more.

  Generally, in many polymer materials, once oxidation starts, oxidative degradation occurs successively in a chain, resulting in a decrease in the function of the polymer material. Therefore, the photocurable thermosetting resin composition of the present invention includes In order to prevent oxidation, (1) the radical scavenger (G-1) or / and (2) the generated peroxide that invalidates the generated radical is decomposed into harmless substances, and no new radical is generated. An antioxidant (G) such as a peroxide decomposing agent (G-2) can be added.

  Specific examples of the antioxidant (G-1) acting as a radical scavenger include hydroquinone, 4-t-butylcatechol, 2-t-butylhydroquinone, hydroquinone monomethyl ether, 2,6-di-t. -Butyl-p-cresol, 2,2-methylene-bis (4-methyl-6-tert-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 1,3,5-tris (3 ′, 5′-di-) phenol-based compounds such as t-butyl-4-hydroxybenzyl) -S-triazine-2,4,6- (1H, 3H, 5H) trione, quinone-based compounds such as methoquinone and benzoquinone, bis (2, , 6,6-tetramethyl-4-piperidyl) - sebacate, and the like amine compounds such as phenothiazine.

  The radical scavenger may be commercially available, for example, ADK STAB AO-30, ADK STAB AO-330, ADK STAB AO-20, ADK STAB LA-77, ADK STAB LA-57, ADK STAB LA-67, ADK STAB LA-68, ADK STAB LA-87 (above, manufactured by Asahi Denka Co., Ltd., trade name), IRGANOX 1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1135, TINUVIN 111FDL, TINUVIN 123, TINUVIN 152, TINUVIN 152, TINUVIN 292, TINUVIN 5100 Special Product name).

  Specific examples of the antioxidant (G-2) acting as a peroxide decomposer include phosphorus compounds such as triphenyl phosphite, pentaerythritol tetralauryl thiopropionate, dilauryl thiodipropionate, di And sulfur compounds such as stearyl 3,3′-thiodipropionate.

The peroxide decomposing agent may be a commercially available one. For example, ADK STAB TPP (manufactured by Asahi Denka Co., Ltd., trade name), Mark AO-412S (manufactured by Adeka Argus Chemical Co., Ltd., trade name), Sumilyzer TPS (Sumitomo Chemical) Company name, product name).
Said antioxidant (G) can be used individually by 1 type or in combination of 2 or more types.

  In general, the polymer material absorbs light, which causes decomposition / degradation. Therefore, the photo-curing thermosetting resin composition of the present invention has the above-mentioned antioxidant in order to take a countermeasure against stabilization against ultraviolet rays. In addition to the agent, an ultraviolet absorber can be used.

  Examples of the ultraviolet absorber include benzophenone derivatives, benzoate derivatives, benzotriazole derivatives, triazine derivatives, benzothiazole derivatives, cinnamate derivatives, anthranilate derivatives, dibenzoylmethane derivatives, and the like. Specific examples of the benzophenone derivative include 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone and 2,4-dihydroxybenzophenone. Is mentioned. Specific examples of benzoate derivatives include 2-ethylhexyl salicylate, phenyl salicylate, pt-butylphenyl salicylate, 2,4-di-t-butylphenyl-3,5-di-t. -Butyl-4-hydroxybenzoate and hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate. Specific examples of the benzotriazole derivative include 2- (2′-hydroxy-5′-t-butylphenyl) benzotriazole, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2 -(2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) -5 -Chlorobenzotriazole, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-amylphenyl) benzotriazole and the like. Specific examples of the triazine derivative include hydroxyphenyl triazine, bisethylhexyloxyphenol methoxyphenyl triazine, and the like.

Ultraviolet absorbers may be commercially available, for example, TINUVIN PS, TINUVIN 99-2, TINUVIN 109, TINUVIN 384-2, TINUVIN 900, TINUVIN 928, TINUVIN 1130, TINUVIN 400, TINUVIN 405, TINUVIN 460, TINUVIN 479 (above, manufactured by Ciba Specialty Chemicals, Inc., trade name).
Said ultraviolet absorber can be used individually by 1 type or in combination of 2 or more types, and is obtained from the photocurable thermosetting resin composition of this invention by using together with the said antioxidant (G). It is possible to stabilize the molded product.

  In the photocurable thermosetting resin composition of the present invention, known and commonly used N-phenylglycines, phenoxyacetic acids, thiophenoxyacetic acids, mercaptothiazole, and the like can be used as chain transfer agents in order to improve sensitivity. . Specific examples of chain transfer agents include, for example, chain transfer agents having a carboxyl group such as mercaptosuccinic acid, mercaptoacetic acid, mercaptopropionic acid, methionine, cysteine, thiosalicylic acid and derivatives thereof; mercaptoethanol, mercaptopropanol, mercaptobutanol, Chain transfer agents having a hydroxyl group such as mercaptopropanediol, mercaptobutanediol, hydroxybenzenethiol and derivatives thereof; 1-butanethiol, butyl-3-mercaptopropionate, methyl-3-mercaptopropionate, 2,2- (Ethylenedioxy) diethanethiol, ethanethiol, 4-methylbenzenethiol, dodecyl mercaptan, propanethiol, butanethiol, pentanethiol, 1-octanethiol, cyclope Tanchioru, cyclohexane thiol, thioglycerol, 4,4-thiobisbenzenethiol like.

A polyfunctional mercaptan-based compound can be used and is not particularly limited. For example, hexane-1,6-dithiol, decane-1,10-dithiol, dimercaptodiethyl ether, dimercaptodiethylsulfide. Aliphatic thiols such as xylylene dimercaptan, 4,4′-dimercaptodiphenyl sulfide, aromatic thiols such as 1,4-benzenedithiol; ethylene glycol bis (mercaptoacetate), polyethylene glycol bis (mercaptoacetate), Propylene glycol bis (mercaptoacetate), glycerin tris (mercaptoacetate), trimethylolethane tris (mercaptoacetate), trimethylolpropane tris (mercaptoacetate), pentaerythrito Poly (mercaptoacetate) polyhydric alcohols such as rutetrakis (mercaptoacetate) and dipentaerythritol hexakis (mercaptoacetate); ethylene glycol bis (3-mercaptopropionate), polyethylene glycol bis (3-mercaptopropionate) ), Propylene glycol bis (3-mercaptopropionate), glycerin tris (3-mercaptopropionate), trimethylolethane tris (mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate), penta Poly (3-mercaptopropionate) of polyhydric alcohols such as erythritol tetrakis (3-mercaptopropionate) and dipentaerythritol hexakis (3-mercaptopropionate) 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 ( Poly (mercaptobutyrate) s such as 1H, 3H, 5H) -trione and pentaerythritol tetrakis (3-mercaptobutyrate) can be used.
Examples of these commercially available products include BMPA, MPM, EHMP, NOMP, MBMP, STMP, TMMP, PMP, DPMP, and TEMPIC (above, manufactured by Sakai Chemical Industry Co., Ltd.), Karenz MT-PE1, Karenz MT-BD1, And Karenz-NR1 (manufactured by Showa Denko KK).

  Further, examples of the heterocyclic compound having a mercapto group acting as a chain transfer agent include mercapto-4-butyrolactone (also known as 2-mercapto-4-butanolide), 2-mercapto-4-methyl-4-butyrolactone, and 2-mercapto. -4-ethyl-4-butyrolactone, 2-mercapto-4-butyrothiolactone, 2-mercapto-4-butyrolactam, N-methoxy-2-mercapto-4-butyrolactam, N-ethoxy-2-mercapto-4- Butyrolactam, N-methyl-2-mercapto-4-butyrolactam, N-ethyl-2-mercapto-4-butyrolactam, N- (2-methoxy) ethyl-2-mercapto-4-butyrolactam, N- (2-ethoxy) Ethyl-2-mercapto-4-butyrolactam, 2-mercapto-5-va Lolactone, 2-mercapto-5-valerolactam, N-methyl-2-mercapto-5-valerolactam, N-ethyl-2-mercapto-5-valerolactam, N- (2-methoxy) ethyl-2-mercapto- 5-valerolactam, N- (2-ethoxy) ethyl-2-mercapto-5-valerolactam, 2-mercaptobenzothiazole, 2-mercapto-5-methylthio-thiadiazole, 2-mercapto-6-hexanolactam, 2 , 4,6-trimercapto-s-triazine (manufactured by Sankyo Kasei Co., Ltd .: trade name: Disnet F), 2-dibutylamino-4,6-dimercapto-s-triazine (manufactured by Sankyo Chemical Co., Ltd .: trade name: Disnet) DB) and 2-anilino-4,6-dimercapto-s-triazine (manufactured by Sankyo Kasei Co., Ltd .: trade name) Sunetto AF), and the like.

  In particular, mercaptobenzothiazole, 3-mercapto-4-methyl-4H-1,2 is a heterocyclic compound having a mercapto group that is a chain transfer agent that does not impair the developability of the photocurable thermosetting resin composition. , 4-triazole, 5-methyl-1,3,4-thiadiazole-2-thiol, 1-phenyl-5-mercapto-1H-tetrazole are preferred. These chain transfer agents can be used alone or in combination of two or more.

  In the photocurable thermosetting resin composition of the present invention, an adhesion promoter can be used in order to improve the adhesion between layers or the adhesion between the resin layer and the substrate. Specific examples include, for example, benzimidazole, benzoxazole, benzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole (trade name: Axel M manufactured by Kawaguchi Chemical Industry Co., Ltd.), 3-morpholinomethyl-1-phenyl-triazole-2-thione, 5-amino-3-morpholinomethyl-thiazole-2-thione, 2-mercapto-5-methylthio-thiadiazole, triazole, tetrazole, benzotriazole, carboxybenzotriazole Amino group-containing benzotriazole, silane coupling agents and the like.

  The photocurable thermosetting resin composition of the present invention preferably contains a thermosetting catalyst when a thermosetting component having two or more cyclic (thio) ether groups in the molecule is used. Examples of such thermosetting catalysts include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole. Imidazole derivatives such as 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole; dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N -Amine compounds such as dimethylbenzylamine and 4-methyl-N, N-dimethylbenzylamine; hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide; and phosphorus compounds such as triphenylphosphine. Examples of commercially available products include 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (both trade names of imidazole compounds) manufactured by Shikoku Kasei Kogyo Co., Ltd., and U-CAT (registered by San Apro). Trademarks) 3503N, U-CAT3502T (all are trade names of blocked isocyanate compounds of dimethylamine), DBU, DBN, U-CATSA102, U-CAT5002 (all are bicyclic amidine compounds and salts thereof), and the like. In particular, it is not limited to these, as long as it is a thermosetting catalyst for epoxy resins or oxetane compounds, or a catalyst that promotes the reaction of epoxy groups and / or oxetanyl groups with carboxyl groups, either alone or in combination of two or more. Can be used. Also, guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino S-triazine derivatives such as -S-triazine and isocyanuric acid adducts and 2,4-diamino-6-methacryloyloxyethyl-S-triazine and isocyanuric acid adducts can also be used. A compound that also functions in combination with the thermosetting catalyst.

  The compounding amount of these thermosetting catalysts is sufficient in a normal quantitative ratio. For example, it is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 15 with respect to (A) the carboxyl group-containing resin. 0.0 part by mass.

  The photocurable thermosetting resin composition of the present invention can be blended with fillers other than hollow silica as long as the properties are not adversely affected. As such a filler, publicly known and commonly used inorganic or organic fillers can be used, and barium sulfate, spherical silica and talc are particularly preferably used. Furthermore, in order to obtain a white appearance and flame retardancy, metal oxides such as titanium oxide and metal hydroxides such as aluminum hydroxide can be used as extender pigment fillers.

  The photocurable thermosetting resin composition of the present invention may further contain a thixotropic agent such as finely divided silica, organic bentonite, montmorillonite, hydrotalcite, etc., if necessary. Organic bentonite and hydrotalcite are preferred as the thixotropic agent over time, and hydrotalcite is particularly excellent in electrical characteristics. Also, thermal polymerization inhibitors, silicone-based, fluorine-based, polymer-based antifoaming agents and / or leveling agents, imidazole-based, thiazole-based, triazole-based silane coupling agents, colorants, rust inhibitors, and more Can be blended with known and commonly used additives such as copper damage inhibitors such as bisphenol and triazine thiol.

  The thermal polymerization inhibitor can be used to prevent thermal polymerization or temporal polymerization of the polymerizable compound. Examples of the thermal polymerization inhibitor include 4-methoxyphenol, hydroquinone, alkyl or aryl-substituted hydroquinone, t-butylcatechol, pyrogallol, 2-hydroxybenzophenone, 4-methoxy-2-hydroxybenzophenone, cuprous chloride, phenothiazine, Chloranil, naphthylamine, β-naphthol, 2,6-di-tert-butyl-4-cresol, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), pyridine, nitrobenzene, dinitrobenzene, picric acid, Examples include 4-toluidine, methylene blue, a reaction product of copper and an organic chelating agent, methyl salicylate, and phenothiazine, a nitroso compound, a chelate of a nitroso compound and Al, and the like.

  The photocurable thermosetting resin composition of the present invention is adjusted to a viscosity suitable for the coating method with, for example, the organic solvent, and on the substrate, a dip coating method, a flow coating method, a roll coating method, a bar coater method, A tack-free dry coating film can be formed by applying the organic solvent contained in the composition at a temperature of about 60 to 100 ° C. by volatile drying (preliminary drying) at a temperature of about 60 to 100 ° C. . Thereafter, the contact pattern (or non-contact pattern) is selectively exposed with an active energy ray through a photomask on which a pattern is formed, or directly exposed with a pattern using a laser direct exposure machine. A resist pattern is formed by development with a 3 to 3% sodium carbonate aqueous solution. Furthermore, by thermosetting the thermosetting component, for example, by heating to a temperature of about 130 to 180 ° C., (A) the carboxyl group-containing resin reacts with the thermosetting component, resulting in heat resistance, chemical resistance, and moisture absorption resistance. Further, a cured film having excellent properties such as adhesion and electrical properties can be formed.

  As the substrate, in addition to a printed circuit board and a flexible printed circuit board in which circuits are formed in advance, paper-phenol resin, paper-epoxy resin, glass cloth-epoxy resin, glass-polyimide, glass cloth / non-woven cloth-epoxy resin , Glass cloth / paper-epoxy resin, synthetic fiber-epoxy resin, all grades (FR-4, etc.) of copper-clad laminates using polyimide, polyethylene, PPO, cyanate, etc., polyimide film, PET film A glass substrate, a ceramic substrate, a wafer plate, or the like can be used.

  Volatile drying performed after applying the photocurable thermosetting resin composition of the present invention is performed using a hot air circulation drying furnace, an IR furnace, a hot plate, a convection oven, or the like (equipped with an air heating heat source using steam). And a method in which hot air in the dryer is brought into countercurrent contact and a method in which the hot air in the dryer is blown onto the support from the nozzle).

After applying the photocurable thermosetting resin composition of the present invention and evaporating and drying as follows, the obtained coating film is exposed (irradiated with active energy rays). In the coating film, the exposed portion (the portion irradiated by the active energy ray) is cured.
As the exposure apparatus used for the active energy ray irradiation, a direct drawing apparatus (for example, a laser direct imaging apparatus that directly draws an image with a laser using CAD data from a computer), an exposure apparatus equipped with a metal halide lamp, and an (ultra) high pressure mercury lamp. , An exposure machine equipped with a mercury short arc lamp, or a direct drawing apparatus using an ultraviolet lamp such as a (super) high pressure mercury lamp.

  The developing method can be a dipping method, a shower method, a spray method, a brush method or the like, and as a developer, potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, Alkaline aqueous solutions such as ammonia and amines can be used.

  The photocurable thermosetting resin composition of the present invention is formed by applying the photocurable thermosetting resin composition in advance to a film such as polyethylene terephthalate and drying it in addition to the liquid direct application method on the substrate. It can also be used in the form of a dry film having a resin layer. The case where the photocurable thermosetting resin composition of this invention is used as a dry film is shown below.

  The dry film has a structure in which a carrier film, a resin layer, and a peelable cover film used as necessary are laminated in this order. The resin layer is a layer obtained by applying and drying the photocurable thermosetting resin composition of the present invention on a carrier film or a cover film. After the resin layer is formed on the carrier film, a cover film is laminated thereon, or a resin layer is formed on the cover film, and this laminate is laminated on the carrier film to obtain a dry film.

As the carrier film, a thermoplastic film such as a polyester film having a thickness of 2 to 150 μm is used.
The resin layer is formed by uniformly applying a photocurable thermosetting resin composition to a carrier film or a cover film with a thickness of 10 to 150 μm using a blade coater, a lip coater, a comma coater, a film coater, and the like, and then drying. .
As the cover film, a polyethylene film, a polypropylene film or the like can be used, but a cover film having a smaller adhesive force than the carrier film is preferable.

  To produce a cured coating on a printed wiring board using a dry film, the cover film is peeled off, the resin layer and the circuit-formed base material are stacked, and bonded together using a laminator, etc., on the circuit-formed base material. A resin layer is formed. If the formed resin layer is exposed, developed, and heat-cured in the same manner as described above, a cured film can be formed. The carrier film may be peeled off either before exposure or after exposure.

  The photocurable thermosetting resin composition of the present invention is used for forming a cured film on a printed wiring board. The cured coating is preferably a development-type permanent insulating coating, and particularly preferably a development-type solder resist or coverlay. In addition, you may use the photocurable thermosetting resin composition of this invention as an interlayer insulation material, a hole filling material, and a solder dam formation material.

  EXAMPLES Hereinafter, the present invention will be described in detail with reference to examples and comparative examples, but the present invention is not limited to the following examples. In the following description, “parts” and “%” are based on mass unless otherwise specified.

Synthesis example 1
Orthocresol novolak type epoxy resin [DICLON N-695 manufactured by DIC, softening point 95 ° C., epoxy equivalent 214, average functional group number 7.6] 1070 g (number of glycidyl groups (total number of aromatic rings)): 600 g of diethylene glycol monoethyl ether acetate 0 mol), 360 g (5.0 mol) of acrylic acid, and 1.5 g of hydroquinone were charged, heated and stirred at 100 ° C., and uniformly dissolved. Next, 4.3 g of triphenylphosphine was charged, heated to 110 ° C. and reacted for 2 hours, then heated to 120 ° C. and reacted for further 12 hours. Into the obtained reaction solution, 415 g of aromatic hydrocarbon (Sorvesso 150) and 534 g (3.0 mol) of methyl-5-norbornene-2,3-dicarboxylic acid anhydride were charged, and reacted at 110 ° C. for 4 hours. After cooling, a cresol novolak-type carboxyl group-containing resin solution having a solid content acid value of 89 mgKOH / g and a solid content of 65% was obtained. This is designated as carboxyl group-containing resin * 1.

Synthesis example 2
In a 5 liter separable flask equipped with a thermometer, a stirrer and a reflux condenser, 1,245 g of polycaprolactone diol (PLACCEL 208, molecular weight 830, manufactured by Daicel Chemical Industries, Ltd.) as a polymer polyol, a dihydroxyl compound having a carboxyl group Dimethylolpropionic acid 201 g as polyisocyanate, 777 g of isophorone diisocyanate as polyisocyanate, 119 g of 2-hydroxyethyl acrylate as hydroxyl-containing (meth) acrylate, p-methoxyphenol and di-t-butyl-hydroxytoluene each of 0 .5 g was added. The mixture was stopped by heating to 60 ° C. while stirring, and 0.8 g of dibutyltin dilaurate was added. When the temperature in the reaction vessel starts to decrease, the mixture is heated again and stirred at 80 ° C., and the reaction is terminated after confirming that the absorption spectrum of the isocyanate group (2280 cm ⁻¹ ) has disappeared in the infrared absorption spectrum. A viscous liquid urethane acrylate compound was obtained. The volatile content was adjusted to 50% by mass using carbitol acetate. A resin solution of a urethane (meth) acrylate compound having a carboxyl group having a solid acid value of 47 mgKOH / g and a nonvolatile content of 50% was obtained. Hereinafter, this is referred to as a carboxyl group-containing resin * 4.

Synthesis example 3
A novolac-type cresol resin (manufactured by Showa Polymer Co., Ltd., trade name “Shonol CRG951”, OH equivalent: 119.4) 119. 4 g, 1.19 g of potassium hydroxide and 119.4 g of toluene were charged, the inside of the system was replaced with nitrogen while stirring, and the temperature was raised by heating. Next, 63.8 g of propylene oxide was gradually added dropwise and reacted at 125 to 132 ° C. and 0 to 4.8 kg / cm ² for 16 hours. Thereafter, the reaction solution was cooled to room temperature, and 1.56 g of 89% phosphoric acid was added to and mixed with the reaction solution to neutralize potassium hydroxide. The nonvolatile content was 62.1% and the hydroxyl value was 182.2 g / eq. A novolak-type cresol resin propylene oxide reaction solution was obtained. This was an average of 1.08 moles of alkylene oxide added per equivalent of phenolic hydroxyl group.
Next, 293.0 g of the resulting novolak-type cresol resin alkylene oxide reaction solution, 43.2 g of acrylic acid, 11.53 g of methanesulfonic acid, 0.18 g of methylhydroquinone and 252.9 g of toluene were mixed with a stirrer, thermometer and air. A reactor equipped with a blowing tube was charged, air was blown at a rate of 10 ml / min, and the reaction was carried out at 110 ° C. for 12 hours while stirring. As the water produced by the reaction, 12.6 g of water was distilled as an azeotrope with toluene. Thereafter, the mixture was cooled to room temperature, and the resulting reaction solution was neutralized with 35.35 g of a 15% aqueous sodium hydroxide solution and then washed with water. Thereafter, toluene was distilled off while substituting 118.1 g of diethylene glycol monoethyl ether acetate with an evaporator to obtain a novolak acrylate resin solution. Next, 332.5 g of the obtained novolac acrylate resin solution and 1.22 g of triphenylphosphine were charged 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, 60.8 g of tetrahydrophthalic anhydride was gradually added and reacted at 95 to 101 ° C. for 6 hours. A resin solution of a carboxyl group-containing photosensitive resin having a solid acid value of 88 mgKOH / g and a nonvolatile content of 71% was obtained. Hereinafter, this is referred to as a carboxyl group-containing resin * 5.

  It mix | blends with the ratio (mass part) shown in Table 1, 2 with the various components shown in the following Table 1, knead | mixes with a 3 roll mill after premixing with a stirrer, and photocurable thermosetting resin composition is carried out. Prepared. The average particle diameter d50 of the hollow filler is a value measured using a laser diffraction / scattering particle size distribution measuring device ("Microtrack MT3200II" manufactured by Nikkiso Co., Ltd.).

＊１：エポキシ樹脂を出発原料とするカルボキシル基含有樹脂、クレゾールノボラック型、固形分６５％、酸価８０ｍｇＫＯＨ／ｇ
＊２：エポキシ樹脂を出発原料とするカルボキシル基含有樹脂、ＺＦＲ−１４０１Ｈ、日本化薬社製ビスフェノールＦ型、固形分６０％、酸価１００ｍｇＫＯＨ／ｇ
＊３：カルボキシル基含有共重合樹脂、サイクロマーＰ（ＡＣＡ）Ｚ２５０、ダイセル・サイテック社製アクリル共重合型、固形分４５％、酸価７０ｍｇＫＯＨ／ｇ
＊４：カルボキシル基含有ウレタン樹脂、固形分５０％、酸価４７ｍｇＫＯＨ／ｇ
＊５：フェノール化合物を出発原料とするカルボキシル基含有樹脂、固形分７１％、酸価８８ｍｇＫＯＨ／ｇ
＊６：光重合開始剤、ＢＡＳＦ社製ＩＲＧＡＣＵＲＥ９０７、２−メチル−１−（４−メチルチオフェニル）−２−モルフォリノプロパン−１−オン
＊７：光重合開始剤、ＢＡＳＦ社製ＩＲＧＡＣＵＲＥ３６９、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
＊８：感光性モノマー、新中村化学社工業製ＮＫエステル Ａ−ＤＰＨ、ジペンタエリスリトールヘキサアクリレート
＊９：感光性モノマー、新中村化学社工業製ＮＫエステル Ａ−ＴＭＰＴ、トリメチロールプロパントリアクリレート
＊１０：熱硬化性成分、ＤＩＣ社製エピクロンＮ−６６０、クレゾールノボラック型エポキシ樹脂、エポキシ当量２０２−２１２ｇ／ｅｑ
＊１１：熱硬化性成分、ジャパンエポキシレジン社製ｊＥＲ８２８、ビスフェノールＡ型エポキシ樹脂、エポキシ当量１８４−１９４ｇ／ｅｑ
＊１２：熱硬化触媒、ＤＣＤＡ、ジシアンジアミド
＊１３：着色剤、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｂｌｕｅ １５：３
＊１４：着色剤、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｙｅｌｌｏｗ１４７
＊１５：中空フィラー、住友スリーエム社製グラスバブルズｉＭ３０Ｋ、中空ガラス、平均粒径１６μｍ
＊１６：中空フィラー、住友スリーエム社製グラスバブルズＫ１、中空ガラス、平均粒径６５μｍ
＊１７：中空フィラー、ポッターズ・バロティーニ社製Ｅｘｔｅｎｄｏｓｐｈｅｒｅｓ ＴＧ、中空ガラス、平均粒径９５μｍ
＊１８：中空フィラー、日揮触媒化成社製スルーリア１１１０、中空シリカの固形分２０ｗｔ％イソプロパノール分散液、中空シリカ、平均粒径５５ｎｍ
＊１９：中空ではないフィラー、堺化学社製Ｂ−３０、硫酸バリウム、平均粒径０．３μｍ
＊２０：中空ではないフィラー、株式会社龍森社製Ｃｒｙｓｔａｌｉｔｅ ３Ｋ、シリカ、平均粒径３４．４μｍ
＊２１：酸化防止剤、ＢＡＳＦ社製ＩＲＧＡＮＯＸ１０１０、ペンタエリスリトールテトラキス［３−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピオネート］
＊２２：消泡剤、共栄社化学社製フローレンＡＣ−９０２、シリコーン系消泡剤
＊２３：溶剤、ジプロピレングリコールモノメチルエーテル

* 1: Carboxyl group-containing resin starting from epoxy resin, cresol novolac type, solid content 65%, acid value 80 mgKOH / g
* 2: Carboxyl group-containing resin starting from epoxy resin, ZFR-1401H, Nippon Kayaku Co., Ltd. bisphenol F type, solid content 60%, acid value 100 mgKOH / g
* 3: Carboxyl group-containing copolymer resin, Cyclomer P (ACA) Z250, acrylic copolymer produced by Daicel-Cytec, solid content 45%, acid value 70 mgKOH / g
* 4: Carboxyl group-containing urethane resin, solid content 50%, acid value 47 mgKOH / g
* 5: Carboxyl group-containing resin starting from a phenol compound, solid content 71%, acid value 88 mgKOH / g
* 6: Photopolymerization initiator, IRGACURE907 manufactured by BASF, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one * 7: Photopolymerization initiator, IRGACURE369, 2-produced by BASF Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1
* 8: Photosensitive monomer, NK ester A-DPH, dipentaerythritol hexaacrylate manufactured by Shin-Nakamura Chemical Co., Ltd. * 9: Photosensitive monomer, NK ester A-TMPT, trimethylolpropane triacrylate manufactured by Shin-Nakamura Chemical Co., Ltd. * 10 : Thermosetting component, Epicron N-660 manufactured by DIC, cresol novolac type epoxy resin, epoxy equivalent 202-212 g / eq
* 11: Thermosetting component, jER828 manufactured by Japan Epoxy Resin, bisphenol A type epoxy resin, epoxy equivalent 184-194 g / eq
* 12: Thermosetting catalyst, DCDA, dicyandiamide * 13: Colorant, C.I. I. Pigment Blue 15: 3
* 14: Colorant, C.I. I. Pigment Yellow147
* 15: Hollow filler, Sumitomo 3M Glass Bubbles iM30K, hollow glass, average particle size 16 μm
* 16: Hollow filler, Sumitomo 3M Glass Bubbles K1, hollow glass, average particle size 65 μm
* 17: Hollow filler, Potters Barotini Extendospheres TG, hollow glass, average particle size 95 μm
* 18: Hollow filler, Julia Catalyzer's Sululia 1110, hollow silica solid content 20 wt% isopropanol dispersion, hollow silica, average particle size 55 nm
* 19: Filler that is not hollow, Sakai Chemical B-30, barium sulfate, average particle size 0.3 μm
* 20: Non-hollow filler, Crystallite 3K manufactured by Tatsumori Co., Ltd., silica, average particle size 34.4 μm
* 21: Antioxidant, IRGANOX 1010 manufactured by BASF, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate]
* 22: Antifoaming agent, Kyoeisha Chemical Co., Ltd. Floren AC-902, silicone-based antifoaming agent * 23: Solvent, dipropylene glycol monomethyl ether

<Sensitivity>
The photocurable thermosetting resin composition for production of printed wiring boards described in Tables 1 and 2 was applied to the entire surface of a circuit pattern substrate having a copper thickness of 35 μm which was washed with water after buffing and dried and screen-printed. It was dried for 30 minutes in a hot air circulation drying oven at 0 ° C. Thereafter, a test piece was irradiated with ultraviolet light having a wavelength of 365 nm with a light quantity of 400 mJ / cm ² using an integrated light meter manufactured by Oak Manufacturing Co., Ltd. through a photomask, and a developer having a spray pressure of 2 kg / cm ² . After developing with (sodium carbonate aqueous solution) for 60 seconds, the number of steps of the remaining coating film was visually determined. The photomask is manufactured by Eastman Kodak Company, Step Tablet No. 2 was used.
<Solder heat resistance>
The evaluation board coated with the rosin flux was dipped in a solder bath set at 260 ° C. in advance, and the flux was washed with denatured alcohol, and then the resist layer was visually evaluated for swelling and peeling. The judgment criteria are as follows.
A: No peeling is observed even after 10 seconds of immersion is repeated 4 times or more. ○: No peeling is observed even if the immersion for 10 seconds is repeated 3 times. Δ: A slight peeling occurs when the immersion is repeated 3 times for 10 seconds. There is swelling and peeling in the cured film within 2 times

<Dielectric constant Dk>
It measured according to JISK6911.
○: Less than 2.5 Δ: 2.5 or more and less than 3.0 ×: 3.0 or more

  As is apparent from Tables 3 and 4, the photocurable thermosetting resin composition of the present invention can form a cured product having a low dielectric constant, and also has high sensitivity and excellent solder heat resistance. It turned out that it can be used conveniently as a composition for formation.

Claims (6)

(A) carboxyl group-containing resin (B) photopolymerization initiator (C) photosensitive monomer (D) thermosetting component, and
(E) A photocurable thermosetting resin composition for producing a printed wiring board, comprising a hollow filler.   2. The photocurable thermosetting resin composition for producing a printed wiring board according to claim 1, wherein an average particle diameter d50 of the (E) hollow filler is in a range of 1 μm to 110 μm.   The photocurable thermosetting resin composition for producing a printed wiring board according to claim 1, wherein the (E) hollow filler is hollow glass or hollow silica.   The dry film for manufacture of the printed wiring board obtained by apply | coating and drying the photocurable thermosetting resin composition for manufacture of the printed wiring board of any one of Claim 1 thru | or 3 to a carrier film.   Photocuring and thermosetting the photocurable thermosetting resin composition for manufacturing a printed wiring board according to any one of claims 1 to 3, or the dry film for manufacturing a printed wiring board according to claim 4. Hardened product obtained.   A printed wiring board having the cured product according to claim 5.