JP2018053215A - Photocurable thermocurable resin composition, dry film, cured article and printed wiring board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photocurable thermocurable resin composition capable of displaying characters or symbols on a cured coated film surface by irradiating different dose of active energy rays.SOLUTION: There is provided a photocurable thermocurable resin composition containing (A) a carboxyl group-containing resin, (B) a photoinitiator, (C) a dye, (D) a reactive diluent, and (E) a thermosetting component, and providing three or more of ΔEab value of a part with sensitivity 0 level and sensitivity 3 level of a cured coated film obtained by irradiating ultraviolet with maximum sensitivity of 7 level to a dried coated film of the photocurable thermocurable resin composition by using Kodak photographic step tablet No.2, conducting development for 60 sec. by using 1 wt% of sodium carbonate solution with spray pressure of 2 kg/cmand then thermally curing by hot blast circulation type drying furnace at 150°C for 60 min.SELECTED DRAWING: None

Description

  The present invention relates to a photocurable thermosetting resin composition, a dry film, a cured product, and a printed wiring board.

  The printed wiring board is usually provided with a solder resist for the purpose of preventing the solder from adhering to unnecessary portions or protecting the printed wiring board from an external environment such as high temperature and high humidity. In consideration of the case where the printed wiring board is repaired, the names and positions of the mounted components may be formed on the printed wiring board with marking ink. For the marking ink, a thermosetting type and a UV curable type mainly formed by pattern printing, or an alkali developing type formed by exposing through a negative film and removing an unexposed portion with an alkaline aqueous solution is used. (Unexamined-Japanese-Patent No. 2002-97239, Unexamined-Japanese-Patent No. 2015-170797). Recently, a technique called laser marking is also used in which the color tone of the irradiated portion is changed by irradiating laser light to display characters, symbols, and the like (Japanese Patent Laid-Open No. 2003-273258, Japanese Patent Laid-Open No. 7). No.-25154, JP-A-7-52536, etc.). However, in any marking ink, since the marking formation process is performed separately from the solder resist formation process, the marking ink is required separately from the solder resist ink, and as a result, the manufacturing process of the printed wiring board is reduced. It is complicated and increases the manufacturing cost.

  If a solder resist formation process and a marking formation process can be performed collectively with respect to said problem, the manufacturing process of a printed wiring board will be simplified and reduction of manufacturing cost can be aimed at. For example, in Japanese Patent Application Laid-Open No. 2015-121653, the amount of bubbles generated in a cured coating film is adjusted by changing the amount of ultraviolet irradiation, and the visibility of identification characters and symbols is improved by changing the light scattering intensity of the cured coating film. A method of manufacturing a circuit board to be improved has been proposed.

JP 2002-97239 A Japanese Patent Laying-Open No. 2015-170797 JP 2003-273258 A Japanese Patent Laid-Open No. 7-25154 JP-A-7-52536 Japanese Patent Laying-Open No. 2015-121653

  However, as proposed in Japanese Patent Application Laid-Open No. 2015-121653, when bubbles are intentionally generated in the solder resist, the bubble-existing portion (marking portion) becomes a bubble during solder reflow or gold plating. There is a case where the resistance is inferior compared with a portion where no solder exists (solder resist portion).

  Accordingly, an object of the present invention is to perform a solder resist forming process and a marking ink forming process in a lump by using a solder resist having both functions of a marking ink, thereby shortening a manufacturing process of a printed wiring board and reducing manufacturing costs. . More specifically, it is to provide a photocurable thermosetting resin composition capable of displaying characters and symbols on the surface of a cured coating film by irradiating active energy rays with different doses.

  In the photocurable thermosetting resin composition comprising a carboxyl group-containing resin, a photopolymerization initiator, a dye, a reactive diluent, and a thermosetting component, the photocurable thermosetting resin composition If the coating film of the product is cured after predetermined development and the ΔEab value of the cured film is 0 or more and the sensitivity is 3 or more, the photocurable thermosetting resin It has been found that the composition can be used as a solder resist ink having the function of a marking ink. The present invention is based on such knowledge.

That is, the photocurable thermosetting resin composition according to the present invention is:
(A) a carboxyl group-containing resin,
(B) a photopolymerization initiator,
(C) dyes,
(D) a reactive diluent, and (E) a thermosetting component,
A photocurable thermosetting resin composition comprising:
Kodak Photographic Step Tablet No. 2 is used to irradiate the dried coating film of the photocurable thermosetting resin composition with ultraviolet rays having a maximum sensitivity of 7 levels, and develop for 60 seconds using a 1 wt% aqueous sodium carbonate solution having a spray pressure of 2 kg / cm ^2. And then the cured coating obtained by heat curing for 60 minutes in a hot air circulating drying oven at 150 ° C. has a ΔEab value of 3 or more in the sensitivity 0 stage and sensitivity 3 stage parts. It is.

  In the embodiment of the present invention, it is preferable that the photocurable thermosetting resin composition can form a marking pattern and a solder resist pattern by performing the exposure and development process once.

  In an embodiment of the present invention, the (C) dye is preferably a dye having a triarylmethane skeleton.

  In an embodiment of the present invention, the (C) dye may be at least one selected from the group consisting of Solvent Blue 5, Basic Blue 7, and Basic Violet 4.

  Moreover, the dry film by another embodiment of this invention has a resin layer obtained by apply | coating and drying the said photocurable thermosetting resin composition to a film, It is characterized by the above-mentioned.

  Moreover, the hardened | cured material by another embodiment of this invention is obtained by hardening the said photocurable thermosetting resin composition or the resin layer of the said dry film, It is characterized by the above-mentioned.

  Furthermore, the printed wiring board by another embodiment of this invention has the said hardened | cured material, It is characterized by the above-mentioned.

  According to the present invention, the photocurable thermosetting resin composition is such that the ΔEab value of the sensitivity 0 stage and the sensitivity 3 stage portion of the cured coating film after predetermined development is 3 or more. Thus, it is possible to realize a photo-curable thermosetting resin composition that can be used as a solder resist having the function of a marking ink. In particular, by including a dye having a triarylmethane skeleton as a dye, a photocurable thermosetting resin capable of displaying letters and symbols on the surface of a cured coating film by irradiating different doses of active energy rays It can be a composition.

[Photo-curable thermosetting resin composition]
The photocurable thermosetting resin composition according to the present invention includes, as essential components, (A) a carboxyl group-containing resin, (B) a photopolymerization initiator, (C) a dye, (D) a reactive diluent, and (E ) A thermosetting component. First, each component which comprises the photocurable thermosetting resin composition by this invention is demonstrated.

<(A) Carboxyl group-containing resin>
The (A) carboxyl group-containing resin contained in the photocurable thermosetting resin composition according to the present invention is used for imparting alkali developability, and a known resin containing a carboxyl group in the molecule is used. Can do. 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. As such a (A) carboxyl group-containing resin, a carboxyl group-containing resin having an epoxy resin as a starting material, a carboxyl group-containing urethane resin having a urethane skeleton, and a carboxyl group-containing copolymer having a copolymer structure of unsaturated carboxylic acid A carboxyl group-containing resin using a resin or a phenol compound as a starting material is preferable. Specific examples include the following resins (1) to (10).

(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) a dibasic acid anhydride such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, etc., on a hydroxyl group present in the side chain by reacting a bifunctional or higher polyfunctional epoxy resin with (meth) acrylic acid A carboxyl group-containing photosensitive resin to which is added. Here, the epoxy resin is preferably solid.
(8) Carboxyl group-containing photosensitivity in which (meth) acrylic acid is reacted with a polyfunctional epoxy resin obtained by epoxidizing the hydroxyl group of a bifunctional epoxy resin with epichlorohydrin, and a dibasic acid anhydride is added to the resulting hydroxyl group. Resin. Here, the epoxy resin is preferably solid.
(9) A cyclic ether such as ethylene oxide or a cyclic carbonate such as propylene carbonate is added to a polyfunctional phenol compound such as novolak, and the resulting hydroxyl group is partially esterified with (meth) acrylic acid, and the remaining hydroxyl group is polyvalent. A carboxyl group-containing photosensitive resin obtained by reacting a basic acid anhydride.
(10) One epoxy group and one or more (meth) acryloyl groups in the molecule of glycidyl (meth) acrylate, α-methylglycidyl (meth) acrylate, etc., in addition to the above-mentioned resins (1) to (9) A carboxyl group-containing photosensitive resin obtained by adding a compound having the following.

  (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 used as a generic term for acrylate, methacrylate, and mixtures thereof, and the same applies to other similar expressions hereinafter.

  (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.

<(B) Photopolymerization initiator>
The (B) photopolymerization initiator contained in the photocurable thermosetting resin composition according to the present invention will be described. As the photopolymerization initiator (B) that can be suitably used in the present invention, an oxime ester photopolymerization initiator having an oxime ester group, an alkylphenone photopolymerization initiator, an α-aminoacetophenone photopolymerization initiator, One or more photopolymerization initiators selected from the group consisting of 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 Irgacure TPO manufactured by BASF Japan and Irgacure 819 manufactured by BASF Japan.

  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.

  The blending amount of the (B) photopolymerization initiator is preferably 0.1 to 30 parts by mass, and 1 to 20 parts by mass with respect to 100 parts by mass of the (A) carboxyl group-containing resin on a solid basis. It is more preferable. By being 0.1 to 30 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 30 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 in combination of two or more. The total amount of such a photopolymerization initiator, photoinitiator assistant, and sensitizer is preferably 35 parts by mass or less with respect to 100 parts by mass of the (A) carboxyl group-containing resin on a solid basis. It can suppress that deep part curability falls by these light absorption as it is 35 mass parts or less.

<(C) Dye>
The photocurable thermosetting resin composition according to the present invention is, as a dye (C), a cured coating film after a predetermined development is performed on the coating film of the photocurable thermosetting resin composition, as described later. A dye having a ΔEab value of 3 or more in the sensitivity 0 stage and the sensitivity 3 stage is included. Examples of such dyes include indigo, indanthrene, perinone orange, and flavanthrone yellow. Among these, dyes having a triarylmethane skeleton can be preferably used.

  As the dye having a triarylmethane skeleton, Methyl blue, Thymol blue, Bromothymolblue, Bromophenol blue, Aniline blue, Solvent blue 5, Basic blue 7, Xylene cyanol, Coomassie brilliant blue G250, Coomassie brilliant blue R250, Brilliant blue FCF, Green S, Malachite green, Fast green FCF, Basic violet 3, Basic violet 4, Methyl violet 2B, Methyl violet 6B, Methyl violet 10B, Crystal vi let lactone, Phenolphthalein, Phenol red, Cresol red, Magenta O, and the like Phloxine. Among the above, Solvent blue 5, Basic blue 7, and Basic violet 4 can be used more preferably. These dyes can be used alone or in combination of two or more.

  (C) As for the compounding quantity of dye, 0.5-10 mass parts is preferable with respect to 100 mass parts of (A) carboxyl group containing resin on solid content basis, More preferably, it is 1-8 mass parts, More preferably, it is. It is preferable that it is 1.5-6 mass parts. By setting it as the range of the said compounding quantity, the difference in the color tone of the part irradiated with the active energy ray of a different dose becomes clear.

  Further, the (C) dye may be used by mixing a pigment.

<(D) Reactive diluent>
Examples of the (D) reactive diluent contained in the photocurable thermosetting resin composition according to the present invention include compounds having two or more ethylenically unsaturated groups in the molecule, and α, β-unsaturated polyhydric alcohol. Examples thereof include compounds obtained by adding saturated carboxylic acids, compounds obtained by adding α, β-unsaturated carboxylic acids to glycidyl group-containing compounds, and the like.

  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 these ethylene oxide adducts or propylene oxide adducts; phenoxy acrylate, bisphenol A diacrylate, and ethylene of these phenols Polyvalent acrylates such as oxide adducts or propylene oxide adducts; glycerin diglycidyl ether, glycerin triglycidyl ether Le, trimethylolpropane triglycidyl ether, polyvalent acrylates of glycidyl ethers such as triglycidyl isocyanurate; and melamine acrylate, and any least one of the respective methacrylates corresponding to the acrylates.

  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 the like, and at least one of each methacrylate corresponding to the acrylate.

  Examples of compounds 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-acryloyloxy) Polyethoxyphenyl) propane, 2-hydroxy-3-acryloyloxypropyl acrylate, and any of the methacrylates corresponding to the acrylate There may be at least one kind. The reactive diluents described above can be used alone or in combination of two or more.

  (D) When a reactive diluent is a photosensitive monomer, the compounding quantity of (D) reactive diluent is 5-100 mass parts with respect to 100 mass parts of (A) carboxyl group-containing resin on a solid content basis. Is preferable, more preferably 10 to 90 parts by mass, and still more preferably 15 to 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.

  Further, as a reactive diluent (D), a photosensitive oligomer may be further added to the photosensitive monomer for the purpose of imparting toughness of a cured coating film. Examples of the photosensitive oligomer include urethane acrylate, polyester acrylate, and epoxy acrylate.

  As the urethane acrylate, U-108A, UA-112P, UA-5201, UA-512, UA-412A, UA-4200, UA-4400, UA-340P, UA-2235PE manufactured by Shin-Nakamura Chemical Co., Ltd., UA-160TM, UA-122P, UA-512, UA-W2, UA-7000, UA-7100, U-6HA, U-6H, U-15HA, UA-32P, U-324A, UA-7200; CN968, CN9006, CN9010 manufactured by Satomer Co., Ltd. CN962, CN963, CN964, CN965, CN980, CN980, CN982, CN983, CN996, CN9001, CN9002, CN9788, CN9873, CN9293, CN9293 N944B85, CN989, CN9008; M-1100, M-1200, M-1210, M-1310, M-1600 manufactured by Toagosei Chemical Industry Co., Ltd .; UN-9000PEP, UN-9200A manufactured by Negami Kogyo Co., Ltd. UN-7600, UN-333, UN-1255, UN-6060PTM, UN-6060P, SH-500B; Kyoeisha Chemical Co., Ltd. AH-600, AT-600; Daicel-Cytech Co., Ltd. Evekril 280, Evekril 284, Evecril 402, Evekril 8402, Evekril 8807, Evekril 9270, Evekril 264, Evekril 265, Evekril 1259, Evekrill 8201, KRM8296, Evekril 294 / 25HD, Evekril 4820, Evekrill 1290, Evekrill 1129 K, KRM8200, Evecryl 5129, Evekril 8210, Evekril 8301, Evekril 8405; UN-3320HA, UN-3320HB, UN-3320HC, UN-3320HS, UN-904, UN-901T, UN-905 manufactured by Negami Kogyo Co., Ltd. , UN-952; Double bond Co. Doublemer 5212, Doublemer 5232B, Doublemer 541, Doublemer 5500, Doublemer 570, Doublemer 583-1, Doublemer 5812, Doublemer 5220, Doublemer 527, Doublemer 5400, Doublemer 553, Doublemer 5700, Doublemer 584 , Dou lemer 5900, Doublemer 5222, Doublemer 528, Doublemer 5405, Doublemer 554, Doublemer 571, Doublemer 588, Doublemer 850, Doublemer 523, Doublemer 530M, Doublemer 5433H, Doublemer 564, Doublemer 576, Doublemer 594, Doublemer 87A, Doublemer 7200, Doublemer 7201M , Doublemer 7210, 88A and the like.

  As the polyester acrylate, Aronix M-6100, M-6200, M-6250, M-6500, M-7100, M-7300K, M-8030, M-8060, M-8100 manufactured by Toa Synthetic Chemical Industry Co., Ltd. , M-8530, M-8560, M-9050; Double bonder 2015, Doubler 2231, TF Doubler 2319, Doublemer 257, Doubler 276, Doubler 276, Doubler 276, Doubler 276, Doubler 276, Doubler 276, Doubler 276, Doubler 276 , Doublemer 285, Doublemer 220, Doublemer 2315 Mention may be made of 100, Doublemer 245, Doublemer 272, Doublemer 278X25, Doublemer 286, Doublemer 2230-TF, Doublemer 2315HM35, Doublemer 246, Doublemer 275, Doublemer 281, Doublemer 287 or the like.

  The epoxy acrylate, the Double bond Co. Doublemer 1283C, Doublemer 1700, Doublemer 1710, Doublemer 186, Doublemer 193-TP50, Doublemer 127-100, Doublemer 129, Doublemer 1701, Doublemer 1720, Doublemer 188, Doublemer 193, Doublemer 127- TP20, Doublemer 156, Doublemer 1702, Doublemer 176-TF, Doublemer 191, Doublemer 128, Doublemer 1636, Doublemer 1703, Doublemer 176TF-5 ublemer 193A-TF, it can be mentioned Doublemer 6MX75, Doublemer 6MX75-E and the like. These photosensitive oligomers can be used alone or in combination of two or more.

<(E) Thermosetting component>
The (E) thermosetting component contained in the photocurable thermosetting resin composition according to the present invention includes blocked isocyanate compounds, amino resins, maleimide compounds, benzoxazine resins, carbodiimide resins, cyclocarbonate compounds, polyfunctional epoxy compounds. In addition, known and commonly used thermosetting resins such as polyfunctional oxetane compounds, episulfide resins, and melamine derivatives can be used. Among these, a preferable thermosetting component has at least one of two or more cyclic ether groups and cyclic thioether groups (hereinafter abbreviated as a cyclic (thio) ether group) in one molecule. It is. There are many commercially available thermosetting components having a cyclic (thio) ether group, and various properties can be imparted depending on the structure.

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

  Examples of the polyfunctional epoxy compound (E-1) include jER828, jER834, jER1001, and jER1004 manufactured by Mitsubishi Chemical Corporation, Epicron 840, Epicron 850, Epicron 1050, Epicron 2055, and Epoto YD manufactured by Tohto Kasei Co., Ltd. -011, YD-013, YD-127, YD-128, D.C. E. R. 317, D.E. E. R. 331, D.D. E. R. 661, D.E. E. R. 664, Sumitomo Epoxy ESA-011, ESA-014, ELA-115, ELA-128, manufactured by Sumitomo Chemical Co., Ltd., A.A. E. R. 330, A.I. E. R. 331, A.I. E. R. 661, A.I. E. R. Bisphenol A type epoxy resin such as 664 (all trade names); jERYL903 manufactured by Mitsubishi Chemical, Epicron 152, Epicron 165 manufactured by DIC, Epototo YDB-400, YDB-500 manufactured by Tohto Kasei Co., Ltd., manufactured by Dow Chemical Of D. E. R. 542, Sumitomo Epoxy ESB-400, ESB-700 manufactured by Sumitomo Chemical Co., Ltd., A.A. E. R. 711, A.I. E. R. Brominated epoxy resins such as 714 (both trade names); jER152 and jER154 manufactured by Mitsubishi Chemical Corporation, and D.C. E. N. 431, D.D. E. N. 438, Epicron N-730, Epicron N-770, Epicron N-865 manufactured by DIC, Epototo YDCN-701, YDCN-704 manufactured by Tohto Kasei Co., Ltd., EPPN-201, EOCN-1025, EOCN manufactured by Nippon Kayaku Co., Ltd. -1020, EOCN-104S, RE-306, Sumitomo Epoxy ESCN-195X, ESCN-220, manufactured by Sumitomo Chemical Co., Ltd. E. R. Novolak type epoxy resins such as ECN-235, ECN-299, etc. (both trade names); Epicron 830 manufactured by DIC, jER807 manufactured by Mitsubishi Chemical Co., Ltd. Epototo YDF-170, YDF-175, YDF-2004 manufactured by Tohto Kasei Co., Ltd. (All trade names) bisphenol F-type epoxy resin; hydrogenated bisphenol A-type epoxy resins such as Epototo ST-2004, ST-2007, ST-3000 (trade name) manufactured by Toto Kasei Co., Ltd .; jER604, Etoto YH-434 manufactured by Tohto Kasei Co., Ltd., Sumitomo Chemical Industries Sumi-Epoxy ELM-120, etc. (all trade names) glycidylamine type epoxy resins; Daicel Corporation Celoxide 2021P etc. (trade names) Alicyclic epoxy resin; YL-933 manufactured by Mitsubishi Chemical Corporation, T.W. manufactured by Dow Chemical Co., Ltd. E. N. , EPPN-501, EPPN-502, etc. (all trade names) trihydroxyphenylmethane type epoxy resin; Mitsubishi Chemical Corporation YL-6056, YX-4000, YL-6121 (all trade names) Type or biphenol type epoxy resin or a mixture thereof; bisphenol S type epoxy resin such as EBPS-200 manufactured by Nippon Kayaku Co., Ltd., EPX-30 manufactured by Asahi Denka Kogyo Co., Ltd., EXA-1514 manufactured by DIC Co., Ltd .; Bisphenol A novolac type epoxy resin such as jER157S (trade name) manufactured by Mitsubishi Chemical Corporation; tetraphenylolethane type epoxy resin such as jERYL-931 (trade name) manufactured by Mitsubishi Chemical Corporation; TEPIC manufactured by Nissan Chemical Industries Ltd. Product name) heterocyclic epoxy resin; diglycid such as Bremer DDT manufactured by NOF Corporation Phthalate resin; Tetraglycidylxylenoylethane resin such as ZX-1063 manufactured by Tohto Kasei Co., Ltd .; ESN-190, ESN-360 manufactured by Nippon Steel Chemical Co., Ltd., HP-4032 manufactured by DIC, EXA-4750, EXA-4700, etc. Naphthalene group-containing epoxy resin; epoxy resin having a dicyclopentadiene skeleton such as HP-7200 and HP-7200H manufactured by DIC; glycidyl methacrylate copolymer epoxy resin such as CP-50S and CP-50M manufactured by NOF Corporation; and cyclohexyl Copolymerized epoxy resin of maleimide and glycidyl methacrylate; epoxy-modified polybutadiene rubber derivative (for example, Epode PB-3600 manufactured by Daicel Corporation), CTBN-modified epoxy resin (for example, YR-102, YR-450 manufactured by Tohto Kasei Co., Ltd.) Etc. 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 (E-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-ethyl -3-Oxetanyl) methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate and oligomers or copolymers thereof, as well as oxetane alcohol And novolac resin, poly (p-hydroxystyrene), cardo type vinyl 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 (E-3) having two or more cyclic thioether groups in the molecule include YL7000 (bisphenol A type episulfide resin) manufactured by Mitsubishi Chemical Corporation and YSLV-120TE manufactured by Toto Kasei Co., Ltd. Can be mentioned. 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 on the solid content basis. In particular, the blending amount of the thermosetting component having two or more cyclic (thio) ether groups in the molecule is cyclic (thio) with respect to 1 equivalent of carboxyl group of (A) carboxyl group-containing resin on a solid basis. The ether group is preferably in the range of 0.5 to 3.0 equivalents, more preferably 0.8 to 2.5 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.

  Moreover, the photocurable thermosetting resin composition according to the present invention may contain an elastomer for the purpose of imparting flexibility and improving brittleness of the cured product. As the elastomer, for example, polyester elastomer, polyurethane elastomer, polyester urethane elastomer, polyamide elastomer, polyesteramide elastomer, acrylic elastomer, and olefin elastomer can be used. In addition, resins in which some or all of the epoxy groups of epoxy resins having various skeletons are modified with carboxylic acid-modified butadiene-acrylonitrile rubber at both ends 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 in combination of two or more.

  In addition, the photocurable thermosetting resin composition according to the present invention may contain a binder polymer for the purpose of improving touch drying property and handling property. Examples of the binder polymer that can be used include polyester polymers, polyurethane polymers, polyester urethane polymers, polyamide polymers, polyesteramide polymers, acrylic polymers, cellulose polymers, polylactic acid polymers, and phenoxy polymers. . These binder polymers can be used alone or in combination of two or more.

  Furthermore, the photo-curable thermosetting resin composition according to the present invention is organic (A) for the synthesis of a carboxyl group-containing resin and the adjustment of the composition, or for the adjustment of the viscosity for application to a substrate or carrier film. A solvent may be included. Examples of the organic solvent 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 in combination of two or more.

  In general, in many polymer materials, once oxidation starts, oxidative degradation occurs sequentially in a chain, resulting in functional deterioration of the polymer material. In order to prevent oxidation, the photocurable thermosetting resin composition according to the present invention includes (1) a radical scavenger that invalidates the generated radical and (2) the generated peroxide decomposed into a harmless substance. An antioxidant such as a peroxide decomposer that prevents the generation of new radicals can be added.

  Specific examples of the antioxidant that acts 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-t-butyl-4-hydroxybenzyl) benzene, 1,3,5-tris (3 ′, 5′-di-t-butyl-4) -Hydroxybenzyl) -S-triazine-2,4,6- (1H, 3H, 5H) trione and other phenolic compounds, quinone compounds such as methoquinone and benzoquinone, bis (2,2,6,6) 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 144, TINUVIN 152, TINUVIN 292, TINUVS 5100 Japan, TINUVIN 5F Japan, Name).

  Specific examples of the antioxidant that acts as a peroxide decomposer include phosphorus compounds such as triphenyl phosphite, pentaerythritol tetralauryl thiopropionate, dilauryl thiodipropionate, distearyl 3,3′- And sulfur compounds such as 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), Sumilizer TPS (Sumitomo Chemical Company name, product name).

  Antioxidants such as the above-mentioned radical scavengers and peroxide decomposers are used alone or in combination of two or more.

  In general, a polymer material absorbs light, thereby causing decomposition and deterioration. Therefore, the photocurable thermosetting resin composition according to the present invention is oxidized to the above-mentioned oxidation in order to take a countermeasure against stabilization of ultraviolet rays. In addition to the inhibitor, 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 benzophenone derivatives 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.

  The above-mentioned ultraviolet absorbers can be used alone or in combination of two or more, and by using in combination with the antioxidant, it is possible to stabilize the cured product of the photocurable thermosetting resin composition. it can.

  The photocurable thermosetting resin composition according to the present invention may contain a chain transfer agent in order to improve sensitivity. As the chain transfer agent, known and commonly used N-phenylglycines, phenoxyacetic acids, thiophenoxyacetic acids, mercaptothiazole and the like can be used. Specific examples include, for example, a chain transfer agent having a carboxyl group such as mercaptosuccinic acid, mercaptoacetic acid, mercaptopropionic acid, methionine, cysteine, thiosalicylic acid and derivatives thereof; mercaptoethanol, mercaptopropanol, mercaptobutanol, mercaptopropanediol, Chain transfer agents having a hydroxyl group such as 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, cyclopentanci Lumpur, 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.

  As a commercial item of a polyfunctional mercaptan compound, for example, BMPA, MPM, EHMP, NOMP, MBMP, STMP, TMMP, PMP, DPMP, and TEMPIC (above, Sakai Chemical Industry Co., Ltd.), Karenz MT-PE1, Examples include Karenz MT-BD1, Karenz-NR1 (manufactured by Showa Denko KK).

  Examples of the heterocyclic compound having a mercapto group that functions 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-vale Lactone, 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); DB), and 2-anilino-4,6-dimercapto-s-triazine (manufactured by Sankyo Kasei Co., Ltd .: trade name Net AF), and the like.

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

  Moreover, in the photocurable thermosetting resin composition according to 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.

  When the thermosetting component having two or more cyclic (thio) ether groups is contained in the molecule as the above-described (E) thermosetting component, a photocurable thermosetting resin is used. It is preferable that a thermosetting catalyst is contained in the composition. 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, the present invention is not limited to these, and any epoxy resin or oxetane compound thermosetting catalyst, or any one that promotes the reaction of at least one of an epoxy group and an oxetanyl group with a carboxyl group, alone or 2 A mixture of seeds or more may 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 blending amount of the thermosetting catalyst is sufficient at a normal quantitative ratio, for example, preferably 0.1 to 20 parts by mass, more preferably 100 parts by mass of the (A) carboxyl group-containing resin on a solid basis. Is 0.5-15.0 parts by mass.

  The photocurable thermosetting resin composition according to the present invention may contain a filler. As the filler, known and commonly used inorganic or organic fillers can be used. In particular, barium sulfate, spherical silica and talc are 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 blending amount of such a filler is preferably 10 to 400 parts by mass, more preferably 150 to 300 parts by mass with respect to 100 parts by mass of the (A) carboxyl group-containing resin on the basis of the solid content.

  The photocurable thermosetting resin composition according to 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, dyes, rust inhibitors, and more Known and commonly used additives such as copper damage prevention agents such as bisphenol-based and triazine thiol-based compounds can be blended.

  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.

[Use of photo-curable thermosetting resin composition]
The above-mentioned photo-curable thermosetting resin composition is adjusted to a viscosity suitable for a coating method using, for example, an organic solvent, and on a substrate, a dip coating method, a flow coating method, a roll coating method, a bar coater method, screen printing. 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. and performing volatile drying (temporary drying). Thereafter, the contact pattern (or non-contact pattern) is selectively exposed with active energy rays through a photomask on which a pattern is formed, or directly exposed with a pattern using a laser direct exposure machine. .3 to 3% aqueous sodium carbonate solution) to form a resist pattern. Subsequently, the resist pattern is heated to, for example, a temperature of about 130 to 180 ° C. to be thermally cured, whereby (A) the carboxyl group-containing resin and (E) the thermosetting component react to produce heat resistance and chemical resistance. A cured film excellent in various properties such as moisture absorption resistance, adhesion, and electrical characteristics can be formed.

In the photocurable thermosetting resin composition according to the present invention, the above-mentioned dried coating film was used as a photomask for Kodak Photographic Step Tablet No. 2 was irradiated with ultraviolet maximum sensitivity for each light amount of 100 to 2000 mJ / cm ² to 100 mJ / cm ² via a (Eastman Kodak Co.) is a seven-stage, 1 wt% sodium carbonate spray pressure 2 kg / cm ² It is characterized in that the ΔEab value is 3 or more at the sensitivity 0 stage and the sensitivity 3 stage portion of the cured coating film obtained by developing with an aqueous solution for 60 seconds and then thermally curing for 60 minutes. Yes. By using a photocurable thermosetting resin composition having a color difference ΔEab value of 3 or more when it is a cured coating, letters and symbols are applied to the surface of the cured coating by irradiating different doses of active energy rays. It is possible to display. Preferably, the ΔEab value is 5 or more. Further, for example, when forming a resist pattern, ultraviolet rays are irradiated with a light amount of 1000 mJ / cm ² using a photomask having different light transmittances of characters and portions other than the characters, and 1 wt with a spray pressure of 2 kg / cm ² . By developing for 60 seconds using a% sodium carbonate aqueous solution and then thermally curing the resist pattern, the difference in color tone between the character part and the part other than the character of the cured coating can be easily confirmed visually. . Therefore, it is possible to realize a photocurable thermosetting resin composition that can be used as a solder resist having the function of a marking ink used for printed wiring boards and the like. The light transmittance of the character part is preferably 10 to 70%, and more preferably 30 to 70%. On the other hand, the preferable light transmittance of a part other than characters is 80 to 100%, and more preferably 90 to 100%.

  As a substrate for forming a coating film by applying a photocurable thermosetting resin composition, in addition to a printed wiring board and a flexible printed wiring board on which a circuit is formed in advance, paper-phenol, paper-epoxy, glass Cloth-epoxy, glass-polyimide, glass cloth / non-woven cloth-epoxy, glass cloth / paper-epoxy, synthetic fiber-epoxy, copper-clad laminate for high-frequency circuits using fluorine, polyethylene, polyphenylene ether, polyphenylene oxide, cyanate ester, etc. All grades (FR-4, etc.) of copper-clad laminates, polyimide films, PET films, glass substrates, ceramic substrates, wafer plates, etc. can be used.

  Volatile drying (temporary drying) of the coating is performed by using hot air circulation drying oven, IR oven, hot plate, convection oven, etc. A method and a method of spraying on a support from a nozzle).

  By performing exposure (irradiation with active energy rays) on the volatilized and dried coating film, the exposed portion (portion irradiated with active energy rays) of the coating film is cured. As an exposure machine used for active energy ray irradiation, an exposure machine equipped with a metal halide lamp, an exposure machine equipped with a (super) high-pressure mercury lamp, or an exposure machine equipped with a mercury short arc lamp can be used.

  As a method for removing the unexposed area (development method), dipping method, shower method, spray method, brush method, etc. can be used. As the developer, potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, Alkaline aqueous solutions such as sodium phosphate, sodium silicate, ammonia and amines can be used.

  In the present invention, in addition to the method of directly applying the liquid photocurable thermosetting resin composition to the substrate, the photocurable thermosetting resin composition is previously applied to a film of polyethylene terephthalate and dried. It can also be used in the form of a dry film having a formed resin layer. The case where the photocurable thermosetting resin composition of this invention is used as a dry film is demonstrated.

  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 according to the present invention may be used as a dry film as described above, or may be used as a liquid. When used as a liquid, it may be one-component or two-component or more. In particular, it is preferable to use two liquids from the viewpoint of storage stability. In the case of two liquids, if the above-mentioned (A) carboxyl group-containing resin is used, it differs even if (B) the photopolymerization initiator and other components are blended in the same preparation as the (A) carboxyl group-containing resin. You may mix | blend with a formulation. In particular, (B) the photopolymerization initiator is preferably blended in the same formulation, and (E) it is preferable to blend in a formulation different from the formulation containing the thermosetting component.

  The photocurable thermosetting resin composition according to the present invention can be suitably 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.

  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 all based on mass unless otherwise specified.

<Synthesis Example 1>
Orthocresol novolak type epoxy resin (DICICLON N-695 made 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: 5. 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, 1245 g of polycaprolactone diol (Placel 208 manufactured by Daicel Corporation, molecular weight 830) as a polymer polyol, and dimethylolpropion as a dihydroxyl compound having a carboxyl group 201 g of acid, 777 g of isophorone diisocyanate as a polyisocyanate, 119 g of 2-hydroxyethyl acrylate as a (meth) acrylate having a hydroxyl group, and 0.5 g each of p-methoxyphenol and di-t-butyl-hydroxytoluene did. 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. This was adjusted to 50% by mass of nonvolatile content using carbitol acetate. In this way, 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 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 obtained 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.

<Synthesis Example 4>
Paragraph of Japanese Patent No. 4376290

In the same manner as in Synthesis Example 5, a mixture of an acid-modified vinyl ester having a solid acid value of 90 mgKOH / g and a nonvolatile content of 61% and a carboxyl group-containing bisphenol A type epoxy acrylate was obtained. Hereinafter, this is referred to as a carboxyl group-containing resin * 6.

<Preparation of a photocurable thermosetting resin composition>
It mix | blends with the ratio (mass part) shown in Table 1 and 2 with the various components shown in the following Table 1 and 2, it knead | mixes with a 3 roll mill after premixing with a stirrer, and photocurable thermosetting resin composition A product was prepared.

In addition, each component * 1- * 34 in Table 1 and 2 is as follows.
* 1: Carboxyl group-containing resin starting from the epoxy resin obtained in Synthesis Example 1, 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 type manufactured by Daicel Ornex, solid content 45%, acid value 70 mgKOH / g
* 4: Carboxyl group-containing urethane resin obtained in Synthesis Example 2, solid content 50%, acid value 47 mgKOH / g
* 5: Carboxyl group-containing resin starting from the phenol compound obtained in Synthesis Example 3, solid content 71%, acid value 88 mgKOH / g
* 6: Mixture of acid-modified vinyl ester and carboxyl group-containing bisphenol A type epoxy acrylate obtained in Synthesis Example 4, solid content 61%, acid value 90 mgKOH / g
* 7: Photopolymerization initiator, IRSFACURE907 manufactured by BASF Japan, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one * 8: Photopolymerization initiator, IRGACURE369E manufactured by BASF Japan 2-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1
* 9: Photopolymerization initiator, KAYACURE DETX-S, 2,4-diethylthioxanthone manufactured by Nippon Kayaku Co., Ltd. * 10: Dye, Solvent blue 5
* 11: Dye, RED500, dye without triarylmethane skeleton * 12: Dye, INDIGO, dye without triarylmethane skeleton * 13: Dye, Basic blue 7, dye with triarylmethane skeleton * 14 : Dye, Basic violet 4, Dye having a triarylmethane skeleton * 15: Dye, MAGENTA O, Dye having a triarylmethane skeleton * 16: Dye, Methyl violet 6B, Dye having a triarylmethane skeleton * 17: Dye Thymol blue, dye having triarylmethane skeleton * 18: Pigment, Pigment green 7
* 19: Pigment, Pigment yellow 147
* 20: Photosensitive monomer, NK ester A-TMPT, manufactured by Shin-Nakamura Chemical Co., Ltd., trimethylolpropane triacrylate * 21: Photosensitive monomer, NK ester A-DPH, manufactured by Shin-Nakamura Chemical Co., Ltd., dipentaerythritol hexaacrylate * 22: Photosensitive oligomer, CN-9178 manufactured by Sartomer Japan, urethane acrylate
* 23: Photosensitive oligomer, Aronix M-6200, manufactured by Toa Gosei Co., Ltd., polyester acrylate * 24: Photosensitive oligomer, EBECRYL 3708, manufactured by Daicel Ornex Co., Ltd., epoxy acrylate
* 25: Thermosetting component, jER828 manufactured by Mitsubishi Chemical Corporation, bisphenol A type epoxy resin, epoxy equivalent 184-194 g / eq
* 26: Thermosetting component, DIC Corporation Epicron N-660, cresol novolac type epoxy resin, epoxy equivalent of 202-212 g / eq
* 27: Thermosetting component, TEPIC manufactured by Nissan Chemical Co., Ltd., triglycidyl isocyanurate, epoxy equivalent of 105 g / eq
* 28: Inorganic filler, Sakai Chemical B-30, barium sulfate * 29: Tatsumori Co., Ltd. Crystallite 3K, silica * 30: Inorganic filler, Fuji talc FG106, Talc * 31: Inorganic filler, Kyowa Chemical Industry Co., Ltd. DHT-4A, hydrotalcite * 32: thermosetting catalyst, DCDA, dicyandiamide * 33: antifoaming agent, Kyoeisha Chemical Co., Ltd., Floren AC-902, silicone-based antifoaming agent * 34: solvent, dipropylene glycol monomethyl ether

<Evaluation of ΔEab value of cured coating film>
Each photocurable thermosetting resin composition was applied to the entire surface of a glass epoxy substrate having a thickness of 1.6 mm by washing and drying after buffing with a screen printing method. Let dry for minutes. Thereafter, Eastman Kodak Co., Ltd., Kodak Photographic Step Tablet No. Maximum sensitivity for each light amount of 100 mJ / cm ² 2 via the up 100 to 2000 mJ / cm ² is irradiated with ultraviolet rays as the seven stages, development for 60 seconds using a 1 wt% aqueous solution of sodium carbonate spraying pressure 2 kg / cm ² Was done. After that, heat curing is performed for 60 minutes in a hot air circulation drying oven at 150 ° C., and the ΔEab values of the sensitivity 0 stage and the sensitivity 3 stage when the maximum sensitivity of the obtained cured coating film is 7 stages of exposure are calculated as Konica. It measured using Minolta Sensing Co. color difference meter CR-2600d. The ΔEab value of the cured coating was as shown in Tables 3 and 4 below.

<Evaluation of visibility>
Each photocurable thermosetting resin composition was applied to the entire surface of a glass epoxy substrate having a thickness of 1.6 mm by washing and drying after buffing with a screen printing method. Let dry for minutes. Thereafter, ultraviolet rays are irradiated with a light amount of 1000 mJ / cm ² using a photomask having a light transmittance of 50% in the character portion and a light transmittance in the portion other than the character of 100%, and 1 wt% with a spray pressure of 2 kg / cm ² . Development was performed for 60 seconds using an aqueous sodium carbonate solution. Then, it heat-cured for 60 minutes with a 150 degreeC hot-air circulation type drying furnace, and the difference in the color tone of the character part of the obtained cured coating film and parts other than a character was evaluated visually. The evaluation criteria were as follows.
○: The color tone of the character part and the part other than the character is clearly different △: The color tone of the character part and the part other than the character is slightly different ×: The color tone of the character part and the part other than the character is slightly different The evaluation results are as follows: As shown in Tables 3 and 4.

<Evaluation of dryness to touch>
Each photocurable thermosetting resin composition was applied to the entire surface of a glass epoxy substrate having a thickness of 1.6 mm by washing and drying after buffing with a screen printing method. Let dry for minutes. The dryness to touch of the obtained dried coating film was evaluated according to the following criteria.
○: The dry coating film is not sticky. Δ: The dry coating film is slightly sticky. X: The dry coating film is clearly sticky. The evaluation results were as shown in Tables 3 and 4 below.

<Developability>
Each photocurable thermosetting resin composition was applied by screen printing to the entire surface of a circuit pattern substrate having a copper thickness of 35 μm that was washed with water and dried after buffing, and 30 minutes in a hot air circulation drying oven at 80 ° C. Drying was performed in three ways of 40 minutes and 50 minutes. Then, development was performed for 60 seconds with a developer (sodium carbonate aqueous solution) having a spray pressure of 2 kg / cm ² , and the developability of the coating film was evaluated according to the following criteria.
○: The dry coating film was completely removed by development. Δ: The dry coating film remained slightly after development. ×: The dry coating film remained clearly after development. The evaluation results are shown in Tables 3 and 4 below. As shown.

<Adhesion>
Each photo-curable thermosetting resin composition is applied to the entire surface of a circuit pattern board having a thickness of 35 μm, washed with water and dried after buffalo polishing, by a screen printing method, and dried for 30 minutes in a hot air circulation drying oven at 80 ° C. I let you. Thereafter, ultraviolet light having a wavelength of 365 nm is irradiated with a light quantity of 700 mJ / cm ² using an integrating light meter manufactured by Oak Manufacturing Co., Ltd. through a photomask, and a 1 wt% sodium carbonate aqueous solution having a spray pressure of 2 kg / cm ² is used. And developed for 60 seconds. Thereafter, the substrate was heat-cured for 60 minutes in a hot air circulation drying oven at 150 ° C. to obtain an adhesion evaluation substrate. The substrate was cross-cut in a grid pattern according to JIS K 5600-5-6, and then the remaining number of grids after a peeling test using a cellophane adhesive tape was evaluated according to the following criteria.
○: The remaining number of grids is 70 or more and 100 or less △: The remaining number of grids is 30 or more and 69 or less ×: The remaining number of grids is 29 or less Evaluation results are shown in Tables 3 and 4 below. As shown.

<Solder heat resistance>
Applying rosin-based flux to a substrate made in the same way as for adhesion evaluation, immersing it in a solder bath set at 260 ° C. for 10 seconds, washing the flux with denatured alcohol, then swelling and peeling of the cured coating film Was visually evaluated. The evaluation criteria were as follows.
○: There is no swelling or peeling in the cured coating film. Δ: There is a slight swelling or peeling in the cured coating film. X: The cured coating film clearly has swelling or peeling. The evaluation results are shown in Tables 3 and 4 below. It was as follows.

  As is clear from Tables 3 and 4, the photo-curable thermosetting resin compositions according to the present invention (Examples 1 to 29) had good results in visibility, and thus different doses of active energy. It turns out that it can form the hardened | cured material which can display a character and a symbol on the cured coating film surface by irradiating a line | wire. In addition, the photocurable thermosetting resin composition according to the present invention is suitable as a composition for forming a solder resist used for printed wiring boards and the like because it has high dryness to touch and developability and excellent solder heat resistance. It can be said that it can be used.

  On the other hand, the photocurable thermosetting resin compositions of Comparative Examples 1 to 3 have poor visibility because the ΔEab value of the cured coating film is less than 3.0. Therefore, even when irradiated with different doses of active energy rays. It can be said that it is difficult to display characters and symbols on the surface of the cured coating film. Moreover, although the comparative example 4 is excellent in visibility since (DELTA) Eab value is 3 or more, since it does not contain the (E) thermosetting component, it turns out that it is inferior to adhesiveness or solder heat resistance.

Claims (7)

(A) a carboxyl group-containing resin,
(B) a photopolymerization initiator,
(C) dyes,
(D) a reactive diluent, and (E) a thermosetting component,
A photocurable thermosetting resin composition comprising:
Kodak Photographic Step Tablet No. 2 is used to irradiate the dried coating film of the photocurable thermosetting resin composition with ultraviolet rays having a maximum sensitivity of 7 levels, and develop for 60 seconds using a 1 wt% aqueous sodium carbonate solution having a spray pressure of 2 kg / cm ^2. And then the cured coating obtained by heat curing for 60 minutes in a hot air circulating drying oven at 150 ° C. has a ΔEab value of 3 or more in the zero-sensitivity and three-sensitivity portions. Curable thermosetting resin composition.   The photocurable thermosetting resin composition according to claim 1, wherein the photocurable thermosetting resin composition can form a marking pattern and a solder resist pattern by performing the exposure and development process once.   The photocurable thermosetting resin composition according to claim 1, wherein the (C) dye is a dye having a triarylmethane skeleton.   The photocurable thermosetting resin composition according to claim 3, wherein the (C) dye is at least one selected from the group consisting of Solvent blue 5, Basic blue 7, and Basic violet 4.   It has a resin layer obtained by apply | coating and drying the photocurable thermosetting resin composition of any one of Claims 1-4 on a film, The dry film characterized by the above-mentioned.   The hardened | cured material obtained by hardening the resin layer of the photocurable thermosetting resin composition of any one of Claims 1-3, or the dry film of Claim 5.   A printed wiring board having the cured product according to claim 6.