JP4994036B2 - Photocurable and thermosetting resin composition and cured product thereof - Google Patents

Description

The present invention relates to a photocurable and thermosetting resin composition (hereinafter referred to as a photocurable / thermosetting resin composition) and a cured product thereof, and in particular, various resist materials for printed wiring boards and multilayer printed wiring boards. Photo- and thermosetting resins useful as coating materials, surface treatment agents, molding materials, adhesives, pressure-sensitive adhesives, printing inks, binders, etc., and for the formation of laminates, optical waveguides, etc. Relates to the composition.
More specifically, the present invention provides a novel light in which a component that volatilizes at the time of curing or use at high temperature or under reduced pressure is reduced by using no photopolymerization initiator or using less than the conventional amount. The present invention relates to a curable / thermosetting resin composition and a cured product thereof.

A photo-curable resin composition that is polymerized by active energy rays such as ultraviolet rays and visible rays has an advantage of rapid curing, and is widely used for paints, solder resist inks, printing inks, adhesives, coating agents, and the like. .
Since this photocurable resin composition does not start polymerization with the active energy ray curable resin alone constituting the composition, it is necessary to use a photopolymerization initiator together. It tends to increase the amount of initiator added.

However, if the amount of the photopolymerization initiator is increased, an unreacted photopolymerization initiator or a decomposition product of the photopolymerization initiator remains in the cured product, and light or heat acts on the cured product. However, there is a problem that a cured product is yellowed or a bad odor is generated due to a volatile component derived from the photopolymerization initiator.
Further, when the amount of the photopolymerization initiator is increased, when the cured product is left in a humidified condition or in a liquid, the unreacted photopolymerization initiator or the like may bleed or contaminate the plating solution, for example. There is a problem such as. In addition, the solder resist ink used in precision machines and the like has a problem that the bleed-out photopolymerization initiator causes a decrease in electrical characteristics.
In addition, when used under high temperatures during soldering, or when used under reduced pressure, such as printed wiring boards used in outer space, unreacted photopolymerization initiator volatilizes and contaminates the terminals. There is a problem of causing poor contact and polluting the surrounding environment.
On the other hand, most of the photopolymerization initiator is a powder, and when a coarse powder is present in the composition or when uniform dispersion is not possible, grains are generated in the cured coating, resulting in poor appearance. There's a problem.

In contrast, JP-A-6-298817 proposes a photocurable resin composition that does not contain a photopolymerization initiator. This photocurable resin composition employs a photopolymerization method via a charge transfer complex formed by combining an unsaturated compound having an electron donating group and an unsaturated compound having an electron accepting group. Maleimide derivatives are exemplified as one of unsaturated compounds having an accepting group.
The composition containing the maleimide derivative disclosed in JP-A-6-298817 can be expected to reduce volatile components by not containing a photopolymerization initiator. However, a large amount of ultraviolet irradiation is required, and the cured film obtained does not have sufficient characteristics.

The object of the present invention is that in a composition containing a maleimide derivative, a volatile component can be reduced by not using a photopolymerization initiator or by reducing the amount of a conventional use amount, and in addition, with a relatively small amount of active energy ray irradiation. An object is to provide a photocurable / thermosetting resin composition of an alkali development type that can be cured.
A further object of the present invention is to provide a printed wiring board in which a cured product made of such a photocurable / thermosetting resin composition, for example, an interlayer insulating layer, a solder resist layer, an optical waveguide layer or the like is formed. It is in.

In order to achieve the above object, according to the first aspect of the present invention, (A) a carboxyl group-containing photosensitive resin, (B) N-methylmaleimide, N-ethylmaleimide, maleimidecarboxylic acid and tetrahydrofurfuryl alcohol Reaction product with N-phenylmaleimide, N- (2-methylphenyl) maleimide, N, N′-methylenebismaleimide, N, N′-ethylenebismaleimide, tris (hydroxyethyl) isocyanurate and maleimidecarboxylic acid Isocyanurate skeleton maleimide ester compound obtained by dehydrating ester, isocyanurate skeleton maleimide urethane compound obtained by urethanization of tris (carbamate hexyl) isocyanurate and maleimide alcohol, isophorone bisurethane bis (N-ethylmaleimi) ), Triethylene glycol bis (maleimidoethyl carbonate), polymaleimide ester compound obtained by dehydrating ester of maleimide carboxylic acid and polyol, polymaleimide ester compound obtained by transesterification of maleimide carboxylic acid ester and polyol, Polymaleimide ester compound obtained by ether ring-opening reaction of maleimide carboxylic acid and polyepoxide, polymaleimide urethane compound obtained by urethanization reaction of maleimide alcohol and polyisocyanate, N, N ′-(4,4′- Diphenylmethane) bismaleimide, N, N ′-(4,4′-diphenyloxy) bismaleimide, N, N′-p-phenylenebismaleimide, N, N′-m-phenylenebismaleimide, N, N′-2 , 4-tri Emissions bismaleimide and N, N'-2,6-tolylene bismaleimide derivative selected from the group consisting of maleimide compounds having two or more epoxy groups and / or oxetanyl groups in a molecule (C), ( D) a radically polymerizable compound having a cyclic ether group selected from the group consisting of a tetrahydrofuran ring, a furan ring, a tetrahydropyran ring, a 1,3-dioxolane ring, a 1,3-dioxane ring and a 1,4-dioxane ring , and (E) A thermosetting catalyst is contained, and the blending ratio of each component is 10 to 60 parts by mass of (B) component and 10 to 100 parts by mass of (C) component with respect to 100 parts by mass of component (A). , (D) component of 5 to 50 parts by weight, (E) component developable photocurable and thermosetting resin composition by an alkaline aqueous solution, characterized in that from 0.1 to 20 parts by providing of That.

Incidentally, the blending ratio of each component, the carboxyl group-containing photosensitive resin (A) 100 parts by mass of (solid content, hereinafter the same) relative to, good Mashiku 30 to 50 parts by weight of maleimide derivative (B) , in a proportion of compound 10 to 100 parts by mass of (C), the radical polymerizable compound (D) a good Mashiku 15-30 parts by weight having two or more epoxy groups and / or oxetanyl groups in one molecule It is desirable to add a photopolymerization initiator at a ratio of 3 parts by mass or less when it is added as necessary.

Further, the photocurable / thermosetting resin composition of the present invention may be used in a liquid state or in the form of a dry film, and can be advantageously used in various fields. It can be advantageously used for forming an interlayer insulating layer and a solder resist layer of a wiring board, and further, a core layer and a cladding layer constituting an optical waveguide.
Therefore, according to the second aspect of the present invention, there is provided a cured product obtained by curing the photocurable / thermosetting resin composition by irradiation with active energy rays and / or heating. A printed wiring board in which an interlayer insulating layer and / or a solder resist layer is formed from the photocurable / thermosetting resin composition, and an optical waveguide layer is formed from the photocurable / thermosetting resin composition. A printed wiring board is provided.

According to the photocurable / thermosetting resin composition containing the maleimide derivative of the present invention, the composition contains a radical polymerizable compound having a cyclic ether group (hereinafter simply referred to as “radical polymerizable compound”). This makes it possible to increase the photocurability of the composition without adding a photopolymerization initiator. As a result, a photopolymerization initiator is not used, or can be used in a smaller amount than the conventional use amount, and thus a resin composition in which components that volatilize at the time of curing or use under high temperature or reduced pressure is reduced. be able to.
In addition, according to the photocurable / thermosetting resin composition of the present invention, a cured product having excellent alkali developability and adhesion to a substrate, and having excellent electroless plating resistance, electrical insulation and the like can be obtained. .
Therefore, the photocurable / thermosetting resin composition of the present invention is useful as a paint, printing ink, adhesive, various resist materials, color filter manufacturing materials, optical waveguide materials, etc. It can be suitably used for applications such as solder resist, interlayer insulating layers of multilayer printed wiring boards, and optical waveguide layers.
In particular, the photocurable / thermosetting resin composition of the present invention that is photocured without a photopolymerization initiator suppresses light loss due to light scattering by the photopolymerization initiator particles and light absorption of the photopolymerization initiator. This is advantageous for the formation of an optical waveguide having excellent optical transmission characteristics.

It is a fragmentary sectional view of an example of a multilayer printed wiring board.

It is a fragmentary sectional view of an example of an optical waveguide part.

  1: wiring board, 2: conductor layer, 3: insulating resin layer, 4: via hole, 5: interlayer conduction hole, 6: conductor layer, 11: substrate, 12: lower cladding layer, 13: core layer, 14: upper part Cladding layer

  As a result of diligent research to solve the above-mentioned problems, the present inventor contains a radically polymerizable compound (D) having a specific structure in a photocurable thermosetting resin composition containing a maleimide derivative. It is found that it is possible to increase the photocurability of the composition without adding a photopolymerization initiator, that is, it can be sufficiently cured even with a relatively small amount of active energy ray irradiation. The present invention has been completed. In addition, the photocurable / thermosetting resin composition of the present invention has two or more carboxyl group-containing photosensitive resins (A) and one molecule in addition to the maleimide derivative (B) and the radical polymerizable compound (D). Since it contains the compound (C) having an epoxy group and / or oxetanyl group, development with a dilute alkaline aqueous solution is possible, and the cured coating film also has excellent adhesion, electroless plating resistance, electrical properties, etc. It will be a thing.

Hereinafter, each component of the photocurable thermosetting resin composition of the present invention will be described.
First, the carboxyl group-containing photosensitive resin (A) used in the present invention will be described.
As the carboxyl group-containing photosensitive resin (A), any resin having an unsaturated group and a carboxyl group can be used, and the resin is not limited to a specific one. Is preferred.
(1) A carboxyl group-containing photosensitive resin obtained by adding an ethylenically unsaturated group as a pendant to a copolymer of an unsaturated carboxylic acid and a compound having an unsaturated double bond.
(2) An unsaturated carboxylic acid is reacted with a copolymer of a compound having an epoxy group and an unsaturated double bond and a compound having an unsaturated double bond, and a polybasic acid anhydride is added to the secondary hydroxyl group produced. A carboxyl group-containing photosensitive resin obtained by reacting a product.
(3) Carboxyl group-containing photosensitivity obtained by reacting a copolymer of an acid anhydride having an unsaturated double bond and a compound having an unsaturated double bond with a compound having a hydroxyl group and an unsaturated double bond. resin.
(4) A carboxyl group-containing photosensitive resin obtained by reacting a polyfunctional epoxy compound with an unsaturated monocarboxylic acid and reacting the resulting secondary hydroxyl group with a polybasic acid anhydride.
(5) A carboxyl group-containing photosensitive resin obtained by further reacting a carboxyl group-containing resin obtained by reacting a hydroxyl group-containing polymer with a polybasic acid anhydride and a compound having an epoxy group and an unsaturated double bond.
(6) A carboxyl group-containing photosensitive resin obtained by further reacting a polybasic acid anhydride with a primary hydroxyl group of a modified oxetane resin obtained by reacting a polyfunctional oxetane compound with an unsaturated monocarboxylic acid.
The said carboxyl group containing photosensitive resin can be used individually or in combination of 2 or more types.

Next, as the maleimide derivative (B) used in the present invention,
(B-1) Monofunctional aliphatic / alicyclic maleimide,
(B-2) monofunctional aromatic maleimide,
(B-3) polyfunctional aliphatic / alicyclic maleimide,
(B-4) There is a polyfunctional aromatic maleimide.

  Examples of the monofunctional aliphatic / alicyclic maleimide (B-1) include N-methylmaleimide, N-ethylmaleimide, and maleimide carboxylic acid and tetrahydrofurfuryl alcohol disclosed in JP-A-11-302278. Examples include reactants.

  Examples of the monofunctional aromatic maleimide (B-2) include N-phenylmaleimide and N- (2-methylphenyl) maleimide.

  Examples of the polyfunctional aliphatic / alicyclic maleimide (B-3) include N, N′-methylene bismaleimide, N, N′-ethylene bismaleimide, tris (hydroxyethyl) isocyanurate and aliphatic / alicyclic Isocyanurate skeleton maleimide ester compound obtained by dehydrating ester of maleic maleimide carboxylic acid, isocyanurate skeleton maleimide urethane compound obtained by urethanization of tris (carbamate hexyl) isocyanurate and aliphatic / alicyclic maleimide alcohol Dehydration of isocyanuric skeleton polymaleimides such as isophorone bisurethane bis (N-ethylmaleimide), triethylene glycol bis (maleimidoethyl carbonate), aliphatic / alicyclic maleimide carboxylic acid and various aliphatic / alicyclic polyols Esterification Or an aliphatic / alicyclic polymaleimide ester compound or aliphatic / alicyclic maleimide obtained by transesterification of an aliphatic / alicyclic maleimide carboxylic acid ester with various aliphatic / alicyclic polyols Aliphatic / alicyclic polymaleimide ester compounds, aliphatic / alicyclic maleimide alcohols and various aliphatic / alicyclic poly compounds obtained by ether ring-opening reaction of carboxylic acid and various aliphatic / alicyclic polyepoxides Examples thereof include aliphatic / alicyclic polymaleimide urethane compounds obtained by urethanization with isocyanate.

  Examples of the polyfunctional aromatic maleimide (B-4) include N, N ′-(4,4′-diphenylmethane) bismaleimide, N, N ′-(4,4′-diphenyloxy) bismaleimide, N, N'-p-phenylene bismaleimide, N, N'-m-phenylene bismaleimide, N, N'-2,4-tolylene bismaleimide, N, N'-2,6-tolylene bismaleimide, maleimide carvone Aromatic polymaleimide ester compounds obtained by esterifying acid and various aromatic polyols or transesterifying maleimide carboxylic acid esters with various aromatic polyols, ethers of maleimide carboxylic acid and various aromatic polyepoxides Aromatic polymaleimide ester compounds obtained by ring-opening reaction, maleimide alcohol and various aromatic polyisocyanates Aromatic polymaleimide urethane compounds obtained by urethanation reaction with anate are included.

In the above-mentioned maleimide derivative (B), using a monofunctional aliphatic / alicyclic maleimide (B-1) or a monofunctional aromatic maleimide (B-2) as a monofunctional maleimide, a cured product can be obtained at a low exposure amount. In order to obtain, it is necessary to use together the polyfunctional (meth) acrylate as a diluent mentioned later. In the present specification, (meth) acrylate means acrylate and / or methacrylate, and the same applies to other similar expressions.
In addition, polyfunctional aromatic maleimide (B-4) is a polyfunctional maleimide, but since it has an aromatic ring in the molecule, it absorbs active energy rays and can be used for a composition requiring high sensitivity. difficult.
On the other hand, polyfunctional aliphatic / alicyclic maleimide (B-3) is preferable because of high curability and excellent physical properties of the cured coating film after irradiation with active energy rays. In particular, a maleimide alkyl carboxylic acid or maleimide alkyl carboxylic acid ester having a C 1-6 alkyl group, more preferably a linear alkyl group, a polyethylene glycol having a number average molecular weight of 100-1000 and / or a number average molecular weight of 100- Fat represented by the following general formula (1) and general formula (2) obtained by dehydrating esterification reaction or transesterification reaction with 1000 polypropylene glycol and / or polytetramethylene glycol having a number average molecular weight of 100 to 1000 The group bismaleimide compound is particularly preferable because it has an excellent balance between curability of the resulting composition and physical properties of the coating film.

  The compounding quantity of such a maleimide derivative (B) is 10-60 mass parts with respect to 100 mass parts of said carboxyl group-containing photosensitive resin (A), Preferably it is a ratio of 30-50 mass parts. When the blending amount of the maleimide derivative (B) is less than 10 parts by mass, sufficient photoreactivity cannot be obtained and pattern formation becomes impossible. On the other hand, when it exceeds 60 mass parts, the developability of a dry coating film will be inferior.

(In the formula, m represents an integer of 1 to 6, n represents a value of 2 to 23, and R ¹ represents a hydrogen atom or a methyl group.)

(In the formula, m represents an integer of 1 to 6, and p represents a value of 2 to 14.)

In the photocurable / thermosetting resin composition of the present invention, in order to obtain sufficient cured coating film properties, the compound (C) having two or more epoxy groups and / or oxetanyl groups in the molecule, That is, a polyfunctional epoxy compound (C-1) and / or a polyfunctional oxetane compound (C-2) is used.
Specific examples of the polyfunctional epoxy compound (C-1) include Epicoat 828, Epicoat 834, Epicoat 1001, Epicoat 1004, Epicron 840, Epicron 850, and Epicron manufactured by Dainippon Ink & Chemicals, Inc. 1050, Epicron 2055, Etototo YD-011, YD-013, YD-127, YD-128 manufactured by Tohto Kasei Co., Ltd., D.C. E. R. 317, D.E. E. R. 331, D.D. E. R. 661, D.E. E. R. 664, Ciba Specialty Chemicals' Araldide 6071, Araldide 6084, Araldide GY250, Araldide GY260, Sumitomo Chemical Industries Sumi-Epoxy ESA-011, ESA-014, ELA-115, ELA-128, Asahi Kasei Corporation 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); Epicoat YL903 manufactured by Japan Epoxy Resin, Epicron 152, Epicron 165 manufactured by Dainippon Ink and Chemicals, Epototo YDB-400, YDB- manufactured by Tohto Kasei Co., Ltd. 500, D.C. 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. Brominated epoxy resins such as 714 (all trade names); Epicoat 152 and Epicoat 154 manufactured by Japan Epoxy Resin Co., Ltd., 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 & Chemicals, Epicoat 807 manufactured by Japan Epoxy Resin, Epototo YDF-170 manufactured by Toto Kasei Co., YDF -175, YDF-2004, bisphenol F type epoxy resin such as Araldide XPY306 manufactured by Ciba Specialty Chemicals (all are trade names); Epotot ST-2004, ST-2007, ST-3000 manufactured by Tohto Kasei Hydrogenated bisphenol A type epoxy resin, such as Epicoat 604 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., Sumitomo Chemical Co., Ltd. Epoxy ELM-120 etc. All are trade names) glycidylamine type epoxy resin; Hydantoin type epoxy resins such as Araldide CY-350 (trade name) manufactured by Ciba Specialty Chemicals; Celoxide 2021 manufactured by Daicel Chemical Industries, Ciba Specialty Chemicals Alicyclic epoxy resins such as Araldide CY175, CY179, etc. (both trade names) manufactured by 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 novolac type epoxy resin such as Epicoat 157S (trade name) manufactured by Japan Epoxy Resin; Epicoat YL-931 manufactured by Japan Epoxy Resin, Araldide 163 manufactured by Ciba Specialty Chemicals, etc. Name) Tetraphenylolethane type Poxy resin; Araldide PT810 manufactured by Ciba Specialty Chemicals, TEPIC manufactured by Nissan Chemical Industries, Ltd. (both are trade names); Diglycidyl phthalate resin such as Bremer DGT manufactured by Nippon Oil &Fats; Tetraglycidylxylenoylethane resin such as ZX-1063 manufactured by Nippon Steel; ESN-190 and ESN-360 manufactured by Nippon Steel Chemical Co., Ltd. Naphthalene groups such as HP-4032, EXA-4750, and EXA-4700 manufactured by Dainippon Ink & Chemicals, Inc. Epoxy resin; Epoxy resin having dicyclopentadiene skeleton such as HP-7200 and HP-7200H manufactured by Dainippon Ink &Chemicals; Glycidyl methacrylate copolymer epoxy resin such as CP-50S and CP-50M manufactured by Nippon Oil &Fats; In addition, cyclohexylmaleimide and glycidyl Copolymerized epoxy resins such methacrylate, and the like, but not limited thereto. These epoxy resins can be used alone or in combination of two or more. Among these, a biphenol type or bixylenol type epoxy resin or a mixture thereof is particularly preferable.

  Furthermore, representative examples of the polyfunctional oxetane compound (C-2) used in the present invention include compounds represented by the following general formula (3) and the following general formula (13).

(In the above general formula (3), R ² is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and P is a linear or branched saturated hydrocarbon having 1 to 12 carbon atoms, having 2 to 2 carbon atoms. 12 linear or branched unsaturated hydrocarbons, aromatic hydrocarbons represented by the following formulas (4), (5), (6), (7) and (8), formulas (9) and (10 A group having a divalent valence selected from linear or cyclic alkylenes containing a carbonyl group represented by formula (11) and aromatic hydrocarbons containing a carbonyl group represented by formulas (11) and (12) .)

(Wherein R ³ represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an aryl group, or an aralkyl group, and R ⁴ represents —O—, —S—, —CH ₂ —, —NH—, —SO ₂ —, —CH (CH ₃ ) —, —C (CH ₃ ) ₂ —, or —C (CF ₃ ) ₂ — is represented, and R ⁵ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Represent.

(In the formula, k represents an integer of 1 to 12.)

(In the formula, R ⁶ has the same meaning as R ^2, and Q is a branched alkylene group having 3 to 12 carbon atoms including the following formula (14), (15), (16), or (17)): Represents aromatic hydrocarbons represented by the general formulas (18), (19), and (20), and l represents the number of functional groups bonded to the residue Q, and represents an integer of 3 or more, Preferably it is an integer of 3-100.)

(In the formula, R ⁷ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group.)
In addition to the above compounds, compounds obtained by copolymerizing (meth) acrylic acid esters derived from oxetane alcohol and (meth) acrylic acid, wherein l in the general formula (13) is 100 or less, can also be used.
The oxetane compound (C-2) as described above can be used alone or in combination of two or more.

  The compound (C) having two or more epoxy groups and / or oxetanyl groups in one molecule as described above improves properties such as adhesion and heat resistance of the solder resist by thermosetting. The blending amount is 10 parts by mass or more and 100 parts by mass or less, and preferably 25 to 60 parts by mass with respect to 100 parts by mass of the carboxyl group-containing photosensitive resin (A). When the compounding amount of the compound (C) having two or more epoxy groups and / or oxetanyl groups in one molecule is less than 10 parts by mass, the crosslink density of the cured coating film is lowered, and the solder heat resistance and electroless resistance are reduced. Plating properties tend to be low. On the other hand, when it exceeds 100 parts by mass, the developability of the dried coating film becomes inferior. In addition, in order to accelerate | stimulate the thermosetting reaction of the compound (C) which has a 2 or more epoxy group and / or oxetanyl group in the said molecule | numerator, the thermosetting catalyst mentioned later can be added.

  Examples of the thermosetting catalyst for the compound (C) having two or more epoxy groups and / or oxetanyl groups in one molecule include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methyl. Imidazole derivatives such as imidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole; dicyandiamide, benzyldimethylamine, 4- (Dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, amine compounds such as 4-methyl-N, N-dimethylbenzylamine, adipic acid hydrazide, sebacic acid hydrazide, etc. Hydrazine compounds; triphenyl Phosphorus compounds such as Sufin the like. 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., U-CAT3503N manufactured by San Apro, 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. It is not particularly limited to these, and may be a thermosetting catalyst or an epoxy group or an oxetanyl group that promotes the reaction with a carboxyl group, and may be used alone or in combination of two or more. . Guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-4,6-diamino-S-triazine, 2 S-triazine derivatives such as -vinyl-4,6-diamino-S-triazine / isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine / isocyanuric acid adduct can also be used, Preferably, a compound that also functions as an adhesion promoter is used in combination with the thermosetting catalyst. The amount of the thermosetting catalyst is sufficient in a normal quantitative ratio, for example, 0.1 to 20 parts by mass, preferably 0.5 to 15 parts per 100 parts by mass of the carboxyl group-containing photosensitive resin (A). The ratio is 0.0 part by mass.

The cyclic ether group in the radical polymerizable compound (D) used in the present invention is a tetrahydrofuran ring, a furan ring, a tetrahydropyran ring, a 1,3-dioxolane ring, a 1,3-dioxane ring, or a 1,4-dioxane ring. Among them, a tetrahydrofuran ring is preferable.
Accordingly, the radically polymerizable compound (D) used in the present invention is particularly preferably a radically polymerizable compound having a tetrahydrofuran ring , and the detailed reason is unclear, but photocurable and thermosetting using these. The resin composition has very high curability.

  In addition, the radically polymerizable compound as used in the field of this invention means the compound which has a radically polymerizable group. Here, the radical polymerizable group is a group that undergoes radical chain reaction, and specifically includes (meth) acryloyl group, (meth) acrylamide group, (meth) allyl group, vinyl group, maleimide group, fumarate. There are an acid group, an itaconic acid group, a maleic acid group, and the like. In particular, a (meth) acryloyl group has high curability and is effective. In the present specification, (meth) acryloyl group, (meth) acrylamide group and (meth) allyl group are respectively acryloyl group and / or methacryloyl group, acrylamide group and / or methacrylamide group, allyl group and / or methallyl. Means a group.

Thus, by using the radically polymerizable compound having a cyclic ether group together with the carboxyl group-containing photosensitive resin (A) and the maleimide derivative (B), a photopolymerization initiator is not used, or more than conventionally. With a small amount of photopolymerization initiator used, a cured coating film having excellent characteristics can be obtained even with a smaller amount of UV irradiation.

  As such a radically polymerizable compound (D), TC-110S (trade name) manufactured by Nippon Kayaku Co., Ltd., which is an acrylate of tetrahydrofurfuryl alcohol ε caprolactam, and Osaka Organic Chemical Co., Ltd., which is tetrahydrofurfuryl acrylate Company-made biscort # 150 (trade name) and the like are listed as commercial products.

Furthermore, the radically polymerizable compound (D) is, for example, a method of reacting the following three components (D-1) to (D-3) (first method), or the following (D-1) and (D -4) can be synthesized by a method of reacting the compound (second method).
(D-1) a compound having a cyclic ether group and a hydroxyl group,
(D-2) organic polyisocyanate,
(D-3) a compound having a hydroxyl group and a radical polymerizable group,
(D-4) A compound having an isocyanate group and a radical polymerizable group.

Here, examples of the compound (D-1) having a cyclic ether group and a hydroxyl group include alcohols having a tetrahydrofuran ring such as tetrahydrofurfuryl alcohol and mono-ε-caprolactone adduct of tetrahydrofurfuryl alcohol.
Moreover, alcohols having a tetrahydropyran ring such as tetrahydropyran-2-methanol and mono-ε-caprolactone adduct of tetrahydropyran-2-methanol can be mentioned.
Furthermore, it has a dioxolane ring such as a condensate of 2,2-dimethyl-3-oxypropanal and ethylene glycol, or a mono-ε-caprolactone adduct of a condensate of 2,2-dimethyl-3-oxypropanal and ethylene glycol. Examples include alcohols.
And further, the amine compounds having a cyclic ether group such as te tiger tetrahydrofurfuryl amine, but and the like, but is not limited thereto.

  Examples of the organic polyisocyanate compound (D-2) include aliphatic isocyanates such as trimethylene diisocyanate and hexamethylene diisocyanate; aromatic isocyanates such as m-phenylene diisocyanate and p-phenylene diisocyanate; 2,4-tolylene diene. Modified polyisocyanates such as isocyanate trimer, hexamethylene diisocyanate trimer, isophorone diisocyanate trimer, etc .; urethanation of the above polyisocyanates with polyols such as polyethylene glycol, polytetramethylene glycol, trimethylolpropane Examples thereof include polyisocyanates to be obtained, but are not limited thereto.

Examples of the compound (D-3) having a hydroxyl group and a radical polymerizable group include 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate.
Moreover, the reaction material of a monoepoxy compound and (meth) acrylic acid, for example, 2-hydroxy-3-octyloxypropyl (meth) acrylate, 2-hydroxy-3-lauryloxypropyl (meth) acrylate, etc. are mentioned.
Furthermore, a reaction product of a polyfunctional epoxy compound and (meth) acrylic acid or a (meth) acrylic acid dimer (with respect to two or more epoxy groups of the polyfunctional epoxy compound, (meth) acrylic acid or (meth) acrylic acid A compound obtained by reacting a dimer with each other, that is, a compound obtained by reacting 1 mol of a polyfunctional epoxy compound and (meth) acrylic acid or a (meth) acrylic acid dimer in a ratio of 2 mol or more), for example, bisphenol A diglycidyl ether / (meth) acrylic acid = 1/2 (mole) reactant, bisphenol F diglycidyl ether / (meth) acrylic acid = 1/2 (mole) reactant, and the like. Although the compound mentioned above is an adduct of (meth) acrylic acid, the compound which added the (meth) acrylic acid dimer to the epoxy compound can also be used.
In addition, the compound (D-3) having a hydroxyl group and a radical polymerizable group is not limited to the compounds listed here.

  Examples of the compound (D-4) having an isocyanate group and a radical polymerizable group include methacryl isocyanate, 2-methacryloyloxyethyl isocyanate, 2-hydroxyethyl (meth) acrylate, and 2-hydroxypropyl (meth). Examples thereof include a 1: 1 addition reaction product with a (meth) acrylate having a hydroxyl group such as acrylate.

  In particular, a composition containing a radical polymerizable compound (D) obtained by using (meth) acrylate compounds is preferable because of high curability.

Reaction (first method) of a compound (D-1) having a cyclic ether group and a hydroxyl group, an organic polyisocyanate (D-2), a compound (D-3) having a hydroxyl group and a radical polymerizable group, and The reaction (second method) of the compound (D-1) with the compound (D-4) having an isocyanate group and a radical polymerizable group is not particularly limited, but is synthesized by a known urethanization reaction.

These reactions are preferably performed in a nitrogen atmosphere, for example, in a temperature range of room temperature to 90 ° C., and a catalyst is used. In the said 1st method, the compound (D-1) which has a cyclic ether group and a hydroxyl group with respect to 1 equivalent of isocyanate groups of organic polyisocyanate (D-2), and the compound which has a hydroxyl group and a radically polymerizable group ( The total of hydroxyl groups in D-3) is desirably 0.9 to 1.2 equivalents, and preferably 1.0 to 1.1 equivalents.

In the second method, the hydroxyl group of the compound (D-1) having a cyclic ether group and a hydroxyl group with respect to 1 equivalent of the isocyanate group of the compound (D-4) having an isocyanate group and a radical polymerizable group. Is desirably 0.9 to 1.2 equivalents, and preferably 1.0 to 1.1 equivalents.

  Examples of the catalyst used for the addition reaction between the hydroxyl group and isocyanate include, for example, organic titanium compounds such as tetrabutyl titanate, tetrapropyl titanate, and tetraethyl titanate, and organic tin compounds such as tin octylate, dibutyltin oxide, and dibutyltin laurate. In addition, stannous iodide or the like can be used. The amount of catalyst added is preferably in the range of 10 to 10,000 ppm with respect to the total charge.

  Further, as a reaction solvent, a compound having a radical polymerizable group that does not contain active hydrogen such as a hydroxyl group, an amino group, or a mercapto group, and / or an organic solvent that does not contain active hydrogen such as a hydroxyl group, an amino group, or a mercapto group are used. May be. Examples of the organic solvent include aromatic hydrocarbons such as toluene, ethylbenzene, tetralin, cumene, and xylene; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; formate ester, methyl acetate, ethyl acetate, and n-acetate. Examples include esters such as butyl, but are not limited thereto.

  In any of the above reactions, it is desirable to use a radical polymerization inhibitor for the purpose of suppressing the polymerization of the radical polymerizable group. Examples of the radical polymerization inhibitor include phenolic compounds such as hydroquinone, t-butylhydroquinone, methoquinone, 2,4-dimethyl-6-t-butylphenol, catechol, t-butylcatechol; phenothiazine, p-phenylenediamine, diphenylamine Examples thereof include copper complexes such as copper dimethyldithiocarbamate, copper diethyldithiocarbamate, and copper dibutyldithiocarbamate. These polymerization inhibitors can be used alone or in combination of two or more. You can also. The addition amount of the polymerization inhibitor is preferably in the range of 10 to 10,000 ppm with respect to the total charge.

Essential components of the carboxyl group-containing photosensitive resin (A), maleimide derivative (B), compound (C) having two or more epoxy groups and / or oxetanyl groups in one molecule, and radical polymerizable compound (D) In the photocurable / thermosetting resin composition of the present invention contained as a photopolymerization initiator, it is not always necessary to add a photopolymerization initiator, but the effect of the present invention is not impaired when curing with a smaller exposure amount is required. Within the range, a photopolymerization initiator can be blended as needed to improve photocurability.
Examples of the photopolymerization initiator include benzoin and benzoin alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy Acetophenones such as 2-phenylacetophenone and 1,1-dichloroacetophenone; 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinoaminopropanone-1, 2-benzyl-2-dimethylamino- Aminoacetophenones such as 1- (4-morpholinophenyl) -butan-1-one and N, N-dimethylaminoacetophenone; 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthone Anthraquinones such as laquinone; thioxanthones such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone and 2,4-diisopropylthioxanthone; ketals such as acetophenone dimethyl ketal and benzyldimethyl ketal; benzoylper Organic peroxides such as oxide and cumene peroxide; 2,4,5-triarylimidazole dimer; Riboflavin tetrabutyrate; Thiols such as 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole 2,4,6-tris-s-triazine; organic halogen compounds such as 2,2,2-tribromoethanol and tribromomethylphenylsulfone; benzophenone, 4,4'-bisdiethyl Examples include benzophenones such as aminobenzophenone or xanthones; 2,4,6-trimethylbenzoyldiphenylphosphine oxide; oximes such as 2- (acetyloxyiminomethyl) thioxanthen-9-one. These known and commonly used photopolymerization initiators can be used alone or as a mixture of two or more thereof. Further, N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, pentyl-4- Photoinitiator aids such as tertiary amines such as dimethylaminobenzoate, triethylamine, triethanolamine can be added. Further, a titanocene compound such as CGI-784 (manufactured by Ciba Specialty Chemicals Co., Ltd.) having absorption in the visible light region can also be added to promote the photoreaction. Particularly preferred photopolymerization initiators are 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinoaminopropanone-1, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl)- Butane-1-one, 2- (acetyloxyiminomethyl) thioxanthen-9-one and the like, but is not limited to these, and absorbs light in the ultraviolet or visible region, and (meth) acryloyl As long as it allows radical polymerization of unsaturated groups such as groups, it is not limited to photopolymerization initiators and photoinitiator aids, and can be used alone or in combination. Furthermore, when an oxime-based photopolymerization initiator such as 2- (acetyloxyiminomethyl) thioxanthen-9-one is used, the sensitivity becomes high, so that it can be applied to a laser direct imaging method. .

  The blending amount of the photopolymerization initiator (the total amount when photoinitiator assistants are used) is 3 parts by mass or less, more preferably 2 parts per 100 parts by mass of the carboxyl group-containing photosensitive resin (A). A proportion of less than or equal to parts by mass is desirable. This is because if the photopolymerization initiator is added in a larger amount than the above range, the amount of the volatile component increases and the effect of the present invention is impaired.

  In the photocurable / thermosetting resin composition of the present invention, a diluent comprising a photopolymerizable monomer and / or an organic solvent can be blended as necessary. The purpose of use of the diluent is, in the case of a photopolymerizable monomer, to dilute the photosensitive component to make it easy to apply and to enhance the photopolymerizability. On the other hand, in the case of an organic solvent, the photosensitive component is dissolved and diluted to make it easy to apply as a liquid, and the film is formed by drying to enable contact exposure. Therefore, depending on the diluent used, either a contact method or a non-contact exposure method in which the photomask is in close contact with the coating film is used.

  Furthermore, when monofunctional aliphatic / alicyclic maleimide (B-1) or monofunctional aromatic maleimide (B-2) is used as the maleimide derivative (B), it is difficult to achieve high sensitivity as described above. Therefore, a photopolymerizable monomer as a diluent is used.

  Representative photopolymerizable monomers include hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate; mono- or di-glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol. Acrylates; acrylamides such as N, N-dimethylacrylamide, N-methylolacrylamide, N, N-dimethylaminopropylacrylamide; aminoalkyl acrylates such as N, N-dimethylaminoethyl acrylate and N, N-dimethylaminopropyl acrylate Hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, tris-hydroxyethyl isocyanurate Polyhydric alcohols such as polyhydric acrylates such as these ethylene oxide adducts or propylene oxide adducts; phenoxy acrylate, bisphenol A diacrylate, and acrylates such as ethylene oxide adducts or propylene oxide adducts of these phenols Acrylates of glycidyl ethers such as glycerin diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, triglycidyl isocyanurate; and melamine acrylate and / or methacrylates corresponding to the acrylate, etc. .

  Examples of the organic solvent include 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 and triethylene glycol monoethyl ether; esters such as ethyl acetate, butyl acetate and acetic acid esterified products of the above glycol ethers; ethanol, propanol, ethylene Alcohols such as glycol and propylene glycol; aliphatic hydrocarbons such as octane and decane; petroleum ether, petroleum naphtha, hydrogenated petroleum Sa, and petroleum solvents such as solvent naphtha.

  Such a diluent is used singly or as a mixture of two or more. When a photopolymerizable monomer is used, the preferred amount of use is 100 parts by weight of the carboxyl group-containing photosensitive resin (A). The ratio of 10 to 60 parts by mass, preferably 15 to 50 parts by mass is desirable, and when it is used in a larger amount than this, it is not preferable because the dryness to touch of the dried coating film deteriorates. On the other hand, the amount of the organic solvent used is not limited to a specific ratio, but a range of about 30 to 300 parts by mass with respect to 100 parts by mass of the carboxyl group-containing photosensitive resin (A) is appropriate and selected. It can set suitably according to the application | coating method to perform.

Further, the photocurable / thermosetting resin composition of the present invention has a dielectric constant and a dielectric loss tangent of the cured product without causing deterioration of various properties such as applicability and heat resistance depending on the use. In order to reduce the amount, a spherical porous filler can be blended. Examples of the material for the spherical porous filler include silica and crosslinked resin.
When a normal filler is added to the photocurable / thermosetting resin composition, the dielectric constant and dielectric loss tangent of the cured product are governed by the dielectric constant and dielectric loss tangent of the filler, but when a spherical porous filler is added. Since the air is included in the holes, the dielectric properties can be lowered. In order to be able to include air in this way, the average particle size of the spherical porous filler is desirably 1 to 15 μm, more preferably 1 to 10 μm, and the oil absorption of the spherical porous filler is It is desirable that the amount is about 100 to 500 ml / 100 g, preferably 150 to 300 ml / 100 g.
The blending ratio of such a spherical porous filler is 5 parts by mass or more and 100 parts by mass or less, preferably 50 parts by mass or less per 100 parts by mass of the carboxyl group-containing photosensitive resin (A).

The photocurable / thermosetting resin composition of the present invention can be blended with epoxidized polybutadiene and spherical urethane beads as required within the range not impairing the effects of the present invention.
Epoxidized polybutadiene is blended for the purpose of imparting flexibility and toughness. Examples of the epoxidized polybutadiene include Epolide PB3600 and PB4700 manufactured by Daicel Chemical Industries, Ltd. The blending amount is preferably 5 to 50 parts by mass per 100 parts by mass of the carboxyl group-containing photosensitive resin (A). .
The spherical urethane beads are blended with an average particle diameter of 1 to 15 μm for the purpose of imparting flexibility and low warpage. The amount of the spherical urethane beads is preferably 5 to 100 parts by mass per 100 parts by mass of the carboxyl group-containing photosensitive resin (A).

  If necessary, the photocurable / thermosetting resin composition of the present invention may further include barium sulfate, barium titanate, silicon oxide powder, finely divided silicon oxide, amorphous silica, crystalline silica, fused silica, spherical Known and commonly used inorganic fillers such as silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, mica and the like can be used alone or in combination of two or more. These are used for the purpose of suppressing curing shrinkage of the coating film and improving properties such as adhesion and hardness. The compounding amount of the inorganic filler is 10 to 300 parts by mass, preferably 30 to 200 parts by mass, per 100 parts by mass of the carboxyl group-containing photosensitive resin (A).

  The photo-curable / thermosetting resin composition of the present invention is further known as phthalocyanine blue, phthalocyanine green, iodin green, disazo yellow, crystal violet, titanium oxide, carbon black, naphthalene black, etc. Conventional colorants, known conventional thermal polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, t-butylcatechol, pyrogallol, phenothiazine, etc., known conventional thickeners such as finely divided silica, organic bentonite, montmorillonite, silicone-based, fluorine-based In addition, known and conventional additives such as polymer-based antifoaming agents and / or leveling agents, imidazole-based, thiazole-based, triazole-based silane coupling agents, and the like can be blended.

  The photocurable / thermosetting resin composition of the present invention can be obtained by blending each of the above-described blending components, preferably in the above-described ratio, and uniformly mixing, dissolving, dispersing, and the like with a roll mill or the like. This resin composition is usually liquid, but may be a dry film.

  For producing a dry film, for example, a roll coater, a doctor bar, a wire bar method, a dipping method, a spin coating method, a gravure method, a doctor blade method, etc. are used on a base film (release film). After applying the photocurable / thermosetting resin composition of the present invention, it can be obtained by drying in a drying oven set at about 60 to 100 ° C. and pasting a release film or the like as necessary. At this time, the thickness of the dry coating film on the base film is adjusted to 5 to 160 μm, preferably 10 to 60 μm. As said base film, films, such as a polyethylene terephthalate and a polypropylene, are used suitably.

  The photo-curable / thermosetting resin composition of the present invention having the above composition is diluted as necessary to adjust the viscosity to be suitable for the coating method. Is applied by an appropriate method such as screen printing method, curtain coating method, spray coating method, roll coating method, spin coating method, etc., and the organic solvent contained in the composition is volatilized and dried at a temperature of about 60 to 100 ° C., for example. Thus, a coating film can be formed. Then, it can be selectively exposed with active energy rays through a photomask on which the pattern has been formed, and the unexposed area can be developed with a dilute alkaline aqueous solution to form a resist pattern. A cured film (solder resist film) excellent in adhesion, electroless plating resistance, and electrical properties is formed by final curing (main curing) only by irradiation with active energy rays or heat curing.

As the alkaline aqueous solution, alkaline aqueous solutions such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia and amines can be used.
As the irradiation light source for photocuring, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a xenon lamp, a metal halide lamp, or the like is appropriate. In addition, laser beams and the like can also be used as active energy rays.

  In addition, when forming the interlayer insulating resin layer of the multilayer printed wiring board using the photocurable / thermosetting resin composition of the present invention, it is adjusted to a viscosity suitable for the coating method as necessary, For example, as shown in FIG. 1, it is applied on the conductor layer 2 of the circuit board 1 formed in advance by a conventionally known method as described above, and is dried at a temperature of about 60 to 100 ° C. as necessary. Then, after forming a tack-free coating film, it is selectively exposed with active energy rays through a negative film in which a light-opaque portion having a predetermined shape such as a black circle is formed, and the unexposed portion is, for example, an alkaline aqueous solution as described above The via hole 4 corresponding to the black circle of the negative film is formed. Then, after drilling predetermined interlayer conduction holes 5 and the like as necessary, a roughening treatment is performed with a roughening agent such as an oxidizing agent, an alkaline aqueous solution, or an organic solvent, and the insulating resin layer 3 is roughened. After the conductor layer is coated on the surface by electroless plating, electrolytic plating, or the like, heat treatment is performed to increase the crosslinking density of the insulating resin layer 3 and to relieve stress. For example, the interlayer insulating resin layer 3 excellent in various properties such as adhesion, electroless plating resistance, and electrical properties can be formed by heating to a temperature of about 140 to 180 ° C. and curing. Thereafter, according to a conventional method, the conductor layer on the surface of the insulating resin layer 3 is etched to form a predetermined circuit pattern, and the conductor layer 6 having a circuit formed is formed. Further, such an operation can be sequentially repeated as desired to form an insulating resin layer and a conductor layer having a predetermined circuit pattern alternately built up.

  In addition, the photocurable / thermosetting resin composition of the present invention is not only used as an insulating resin layer in a method for producing a multilayer printed wiring board by the build-up method as described above, but for example, a multilayer by a resin-coated copper foil laminate method. It can also be used for the formation of an insulating resin layer in the production of a printed wiring board, an insulating resin composition for a prepreg used in a lamination press method, and the like.

On the other hand, the photocurable / thermosetting resin composition of the present invention can be used for forming a core layer or a cladding layer of an optical waveguide.
One example of a method for producing an optical waveguide using the photocurable / thermosetting resin composition of the present invention will be described with reference to the drawings.
FIG. 2 is a cross-sectional view of an example of the optical waveguide portion. For example, the photocurable / thermosetting resin composition for the clad layer is adjusted to a viscosity suitable for the coating method if necessary, and applied to the substrate 11 such as a silicon wafer by a conventionally known method, and if necessary, For example, after drying at a temperature of about 60 to 100 ° C. to volatilize the organic solvent, exposure is performed by irradiating active energy rays from above, followed by heat curing in a hot air circulating drying oven at about 140 to 180 ° C. By doing so, the lower clad layer 12 for the optical waveguide is formed. On top of that, after applying a photocurable / thermosetting resin composition for the core layer having a refractive index higher than that of the above composition and drying at a temperature of about 60 to 100 ° C. to volatilize the organic solvent, Expose the active energy beam through the negative film from the top and selectively expose it, and then develop the unexposed area with an alkaline aqueous solution, followed by thermosetting in a hot-air circulating drying oven at about 140 to 180 ° C. Thus, the core layer 13 is formed. Thereafter, the photocurable / thermosetting resin composition for the cladding layer is applied onto the core layer 13 and dried at a temperature of about 60 to 100 ° C. to volatilize the organic solvent. The upper clad layer 14 is formed by irradiating and exposing to a line, and then performing heat curing in a hot-air circulating drying oven at about 140 to 180 ° C. In this way, a multimode type optical waveguide can be manufactured.

The refractive index of the core layer 13 and the cladding layers 12 and 14 is adjusted by adjusting the refractive index of the photocurable / thermosetting resin composition for the core layer and the cladding layer. The refractive index of the photocurable / thermosetting resin composition can be adjusted from the refractive index of the molecule by changing the reaction system and adjusting from the polarization of the binding segment, or by changing the structure of the compound. In the system containing the carboxyl group-containing photosensitive resin (A) as an essential component as in the photocurable / thermosetting resin composition of the present invention, the resin skeleton and the method are more suitable than the method of adjusting the amount of reactive groups. It is easy to adjust the refractive index by adjusting the blending ratio and is highly effective.
In order to increase the refractive index of an organic compound, it is effective to increase molecular refraction or decrease molecular volume. Specifically, a conjugated structure such as a benzene ring, sulfur, —COO—, —COOH, SO ₂ , Introduction of halogen atoms other than CS and fluorine is effective, but introduction of bromine or chlorine is not desirable in terms of environmental burden. On the other hand, in order to lower the refractive index of an organic compound, it is effective to reduce molecular refraction or increase molecular volume. Specifically, an aliphatic ring having 3 to 6 carbon atoms, —OH, —O It is effective to introduce-, -C = C-, NH ₂ and fluorine. However, fluorine-containing polymers have a problem in disposal, and the cost of materials increases. Not desirable.

By the way, in the mano-retarded mode waveguide, the number of modes increases as the width of the core increases and the difference in refractive index between the core layer and the cladding layer increases, thereby improving the light propagation. The difference in refractive index is generally obtained from (n ₁ −n ₀ ) / n ₁ × 100 (%) (where n ₁ represents the refractive index of the core layer and n ₀ represents the refractive index of the cladding layer). However, in a multimode waveguide, the difference in refractive index is preferably 0.5% or more, more preferably 1.0% or more.
The dimension of the core layer varies depending on the difference in the refractive index between the core layer and the clad layer and the desired number of modes. However, when the optical waveguide is used for multimode using a communication wavelength of about 0.85 μm, it is about It is desirable to be in the range of 20-80 μm. In addition, the presence of large particles in the core layer is not preferable because it causes light scattering loss, and it is generally preferable not to include particles of about 1 μm or more.
The printed wiring board on which the optical waveguide is formed is described in, for example, JP-A-6-258537 and International Publication WO 2004 / 095093A1, and the teaching contents thereof are incorporated herein by reference.

  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, “parts” and “%” are based on mass unless otherwise specified.

Synthesis of carboxyl group-containing photosensitive resin (A-1):
330 parts of cresol novolac type epoxy resin (Epicron N-695, manufactured by Dainippon Ink and Chemicals, Epoxy equivalent 220) is placed in a flask equipped with a gas introduction tube, a stirrer, a cooling tube and a thermometer, and carbitol acetate 400 is added. Parts were added and dissolved by heating, and 0.46 part of hydroquinone and 1.38 parts of triphenylphosphine were added. This mixture was heated to 95 to 105 ° C., 108 parts of acrylic acid was gradually added dropwise and reacted for 16 hours. The reaction product was cooled to 80 to 90 ° C., 163 parts of tetrahydrophthalic anhydride was added, and the reaction was allowed to proceed for 8 hours. In the reaction, the acid value and total acid value of the reaction solution are measured by potentiometric titration, followed by the obtained addition rate, and the reaction rate is 95% or more as the end point. The carboxyl group-containing photosensitive resin thus obtained had a nonvolatile content of 60% and a solid acid value of 100 mgKOH / g. Hereinafter, this reaction solution is called varnish A-1.

Synthesis of carboxyl group-containing photosensitive resin (A-2):
322 parts of phenol novolac type epoxy resin (EPPN-201, Nippon Kayaku Co., Ltd., epoxy equivalent 190) is put in a flask equipped with a gas introduction tube, a stirrer, a cooling tube and a thermometer, and 400 parts of carbitol acetate is added. The solution was heated and dissolved, and 0.46 part of hydroquinone and 1.38 parts of triphenylphosphine were added. This mixture was heated to 95 to 105 ° C., 122 parts of acrylic acid was gradually added dropwise and allowed to react for 16 hours. The reaction product was cooled to 80 to 90 ° C., 156 parts of tetrahydrophthalic anhydride was added and allowed to react for 8 hours. In the reaction, the acid value and total acid value of the reaction solution are measured by potentiometric titration, followed by the obtained addition rate, and the reaction rate is 95% or more as the end point. The carboxyl group-containing photosensitive resin thus obtained had a nonvolatile content of 60% and a solid acid value of 96 mgKOH / g. Hereinafter, this reaction solution is called varnish A-2.

Synthesis of carboxyl group-containing photosensitive resin (A-3):
350 parts of bisphenol A type epoxy resin (Japan Epoxy Resin Co., Ltd., Epicoat 1004, epoxy equivalent: 917) and 925 parts of epichlorohydrin were dissolved in 463 parts of dimethyl sulfoxide and then 99% hydroxylated at 70 ° C. with stirring. 61 parts of sodium were added over 100 minutes. After the addition, the reaction was further carried out at 70 ° C. for 3 hours, and after completion of the reaction, 250 parts of water was added and washed with water. After the oil separation, most of the dimethyl sulfoxide and excess unreacted epichlorohydrin were recovered by fractional distillation under reduced pressure, and the reaction product containing the remaining by-product salt and dimethyl sulfoxide was dissolved in 750 parts of methyl isobutyl ketone, and further 30% 10 parts of NaOH was added and reacted at 70 ° C. for 2 hours. After completion of the reaction, water was washed twice with 200 parts of water to separate the oil, and methyl isobutyl ketone was fractionally collected from the oil layer to obtain an epoxy resin having an epoxy equivalent of 318. When the epoxy resin obtained was calculated from the epoxy equivalent, 4.8 out of 5.3 alcoholic hydroxyl groups in the starting material bisphenol A type epoxy resin were epoxidized. 318 parts of this epoxy resin and 351 parts of carbitol acetate were charged into a flask, and heated and stirred at 90 ° C. to dissolve. To this solution, 0.4 part of methylhydroquinone, 72 parts of acrylic acid and 4 parts of triphenylphosphine were added and reacted at 90-95 ° C. for 36 hours to obtain a reaction product having an acid value of 2.2 mgKOH / g. After the reaction solution was cooled to room temperature, 137 parts of tetrahydrophthalic anhydride was added and heated to 85 ° C. The carboxyl group-containing photosensitive resin thus obtained had a nonvolatile content of 60% and a solid content acid value of 96 mgKOH / g. Hereinafter, this reaction solution is referred to as Varnish A-3.

Examples 1-4 and Comparative Examples 1-3
The compounding components shown in Table 1 using the varnishes A-1, A-2, and A-3 obtained by the above synthesis were kneaded with a three-roll mill to obtain a photocurable / thermosetting resin composition. Table 2 shows the characteristic values of each composition.

The performance test method in Table 2 is as follows.

(1) Sensitivity The compositions of the above Examples and Comparative Examples were applied on the entire surface of a glass epoxy substrate by screen printing, dried at 80 ° C. for 20 minutes, allowed to cool to room temperature, and then Kodak Step Tablet No. 2 (21 steps) is used as a photomask, and exposure is performed with an exposure meter (metal halide lamp 7KW2 lamp) manufactured by Oak Manufacturing Co., Ltd. under a reduced pressure so as to be 500, 700, or 900 mJ / cm ² with a 365 nm ultraviolet light quantity meter. Then, a 1% Na ₂ CO ₃ aqueous solution at 30 ° C. was developed for 60 seconds under the condition of a spray pressure of 0.2 MPa, and the gloss level of the cured coating film was visually confirmed. In addition, it shows that it is so sensitive that a numerical value is large.

(2) Electric insulation L / S = 50 μm comb-type electrode The compositions of the above examples and comparative examples were applied to the entire surface using a roll coater manufactured by Pilot Seiko Co., Ltd. It was dried at 80 ° C. for 30 minutes. After cooling to room temperature, Examples 1-4 exposure 700 mJ / cm ^2, Comparative Examples 1 to 3 each were exposed under the conditions of exposure 900,900,500mJ / cm ^2, a hot air circulation type drying oven Was cured at 150 ° C. for 60 minutes to obtain an evaluation sample. A bias voltage of DC 5.5V was applied to this comb-shaped electrode, and the insulation resistance value was measured after being left at a humidity of 85% and a temperature of 130 ° C. for 150 hours.

(3) Resistance to electroless gold plating The composition of each of the above Examples and Comparative Examples was applied to a printed wiring board by a screen printing method and then dried at 80 ° C. for 30 minutes in a hot air circulation type drying furnace. After cooling to room temperature, Examples 1-4 exposure 700 mJ / cm ^2, Comparative Examples 1 to 3 each were exposed under the conditions of exposure 900,900,500mJ / cm ^2, a hot air circulation type drying oven Was cured at 150 ° C. for 60 minutes to obtain an evaluation sample. The obtained evaluation sample was immersed in an acidic degreasing solution at 30 ° C. (20 vol% aqueous solution of METEX L-5B manufactured by Nihon McDermitt), washed with water, and then immersed in an aqueous 14.4 wt% ammonium persulfate solution at room temperature for 3 minutes. After washing with water, it was further immersed in a 10 vol% sulfuric acid aqueous solution for 1 minute at room temperature. Next, this evaluation substrate was immersed in a 30 ° C. catalyst solution (Meltex Co., 10 vol% aqueous solution of metal plate activator 350) for 5 minutes, washed with water, and 85 ° C. nickel plating solution (Meltex Co., Ltd. Nickel plating was performed by immersing in a 20 vol% aqueous solution of plate Ni-865M, pH = 4.6) for 30 minutes, and then immersed in a 10 vol% sulfuric acid aqueous solution for 1 minute at room temperature, followed by washing with water. Next, electroless gold plating is performed by immersing the evaluation sample substrate in a gold plating solution at 95 ° C. (Meltex, 15 vol% of Ourolectroles UP and 3 vol% potassium cyanide aqueous solution, pH = 6) for 30 minutes. Then, it was washed with water, further immersed in warm water at 60 ° C. for 3 minutes, and washed with running water. A cellophane pressure-sensitive adhesive tape was attached to the obtained evaluation sample on which gold plating was applied, and the state of the cured coating film when it was peeled off was confirmed. The judgment criteria are as follows.
○: No abnormality in the cured coating film.
Δ: Some peeling occurred in the cured coating film.
X: The cured coating film was peeled off.

As is clear from the results of Examples 1 to 4 shown in Table 2, the cured product obtained from the photocurable / thermosetting resin composition of the present invention has good sensitivity without using a photopolymerization initiator. As shown, it had excellent electrical insulation resistance and electroless gold plating resistance.
On the other hand, in Comparative Examples 1 and 2, sufficient sensitivity was not obtained, and the obtained cured product was inferior in electric insulation resistance and electroless gold plating resistance. Moreover, in the comparative example 3 using a photoinitiator, the fall of the insulation resistance resulting from the bleedout of a photoinitiator was seen.

  The photocurable / thermosetting resin composition of the present invention includes various coating materials such as paints, printing inks, surface treatment agents, molding materials, adhesives, pressure-sensitive adhesives, binders, various resist materials, materials for producing color filters, It is useful as a material for optical waveguides, and is particularly useful for forming solder resists for printed wiring boards, interlayer insulation layers for multilayer printed wiring boards, optical waveguide layers, and the like.

Claims (6)

(A) Carboxyl group-containing photosensitive resin, (B) N-methylmaleimide, N-ethylmaleimide, reaction product of maleimidecarboxylic acid and tetrahydrofurfuryl alcohol, N-phenylmaleimide, N- (2-methylphenyl) maleimide , N, N′-methylene bismaleimide, N, N′-ethylene bismaleimide, tris (hydroxyethyl) isocyanurate and maleimide carboxylic acid dehydrated esterified maleimide ester compound of tris (carbamate hexyl) ) Isocyanurate skeleton maleimide urethane compound obtained by urethanization of isocyanurate and maleimide alcohol, isophorone bisurethane bis (N-ethylmaleimide), triethylene glycol bis (maleimide ethyl car) Ether), polymaleimide ester compound obtained by dehydrating ester of maleimide carboxylic acid and polyol, polymaleimide ester compound obtained by transesterification reaction of maleimide carboxylic acid ester and polyol, and maleimide carboxylic acid and polyepoxide. Polymaleimide ester compound obtained by ring reaction, polymaleimide urethane compound obtained by urethanization reaction of maleimide alcohol and polyisocyanate, N, N ′-(4,4′-diphenylmethane) bismaleimide, N, N ′ -(4,4'-diphenyloxy) bismaleimide, N, N'-p-phenylene bismaleimide, N, N'-m-phenylene bismaleimide, N, N'-2,4-tolylene bismaleimide and N N'-2,6-Tolylenebisma Maleimide derivative selected from the group consisting of an imide compound having two or more epoxy groups and / or oxetanyl groups in a molecule (C), (D) tetrahydrofuran ring, a furan ring, tetrahydropyran ring, 1,3 dioxolane ring, the radical polymerizable compound having a cyclic ether group selected from the group consisting of 1,3-dioxane ring and 1,4-dioxane rings, and containing (E) a thermosetting catalyst, the mixing ratio of the components However, with respect to 100 parts by weight of component (A), 10 to 60 parts by weight of component (B), 10 to 100 parts by weight of component (C), 5 to 50 parts by weight of component (D), and component (E) 0.1 to 20 parts by mass of a photocurable and thermosetting resin composition developable with an aqueous alkali solution. Before Kira radical polymerizable compound cyclic ether group (D), the photocurable and thermosetting resin composition according to claim 1 tetrahydrofuran ring. Before Kira radical polymerizable compound is a radical polymerizable group (D), the photocurable and thermosetting resin composition of claim 1 which is an acryloyl group and / or a methacryloyl group. It claims 1 to cured product obtained by curing by active energy ray irradiation and / or heating the photocurable and thermosetting resin composition according to any one of 3. A printed wiring board in which an interlayer insulating layer and / or a solder resist layer is formed from the photocurable and thermosetting resin composition according to any one of claims 1 to 3. The printed wiring board by which an optical waveguide layer is formed from the photocurable and thermosetting resin composition as described in any one of Claims 1 thru | or 3.