CN100569825C - Photocurable and thermosetting resin composition and its cured product - Google Patents

Abstract

The present invention provides a photocurable and thermosetting resin composition that can be developed by an alkaline aqueous solution. It does not use a photopolymerization initiator or uses less than the current amount, thereby reducing volatile components, and can be used with less ultraviolet rays. The amount of radiation cures. The composition contains (A) a carboxyl group-containing photosensitive resin, (B) a maleimide derivative, (C) a compound having two or more epoxy groups and/or oxetanyl groups in one molecule, and (D) A radically polymerizable compound having a cyclic ether group or a morpholino group.

Description

Photocurable and thermosetting resin composition and its cured product

technical field

The present invention relates to a photocurable/thermosetting resin composition and its cured product. In particular, it is useful as various resist materials for printed circuit boards, interlayer insulation materials for multilayer printed circuit boards, and as coating materials, Surface treatment agents, molding materials, adhesives, adhesives, printing inks, adhesives, etc., and photocurable and thermosetting resin compositions useful for forming laminates, optical waveguides, etc.

In more detail, the present invention relates to new photocurability of components that can reduce volatilization when curing or using at high temperature or under reduced pressure without using a photopolymerization initiator or using a smaller amount than the current one. Thermosetting resin composition and cured product thereof.

Background technique

A photocurable resin composition that is polymerized by active energy rays such as ultraviolet light or visible light has the advantage of fast curing, and is widely used in coatings, solder resist inks, printing inks, adhesives, coating agents, and the like.

In this photocurable resin composition, the active energy ray-curable resin constituting the composition cannot initiate polymerization alone, so it is necessary to use it in combination with a photopolymerization initiator. The tendency to increase the amount added.

However, when the mixing amount of the photopolymerization initiator increases, there are the following problems: unreacted photopolymerization initiator or decomposition product of the photopolymerization initiator remains in the cured product; The volatile components of the initiator cause the cured product to turn yellow or produce a foul smell.

In addition, when the amount of the photopolymerization initiator mixed is increased, unreacted photopolymerization initiator and the like may seep out or contaminate the plating solution, for example, when the cured product is placed under humidified conditions or in a liquid. In addition, solder resist inks used in precision machinery and the like also have a problem in that electrical characteristics are lowered due to exuded photopolymerization initiators.

Furthermore, when using at high temperatures such as soldering or using under reduced pressure such as printed circuit boards used in space, unreacted photopolymerization initiators may volatilize and contaminate the terminals, resulting in poor contact or contamination. The problem of the surrounding environment.

On the other hand, photopolymerization initiators are often in the form of powders, and if coarse powders are present in the composition or cannot be uniformly dispersed, there is a problem that particles will be generated in the cured coating film, resulting in poor appearance.

In view of these, JP-A-6-298817 proposes a photocurable resin composition not containing a photopolymerization initiator. The photocurable resin composition adopts a photopolymerization method via a charge transfer complex, wherein the charge transfer complex reacts an unsaturated compound having an electron-donating group with an unsaturated compound having an electron-accepting group. Formed in combination, maleimide derivatives can be exemplified as one of the unsaturated compounds having an electron-accepting group.

The maleimide derivative-containing composition disclosed in Japanese Unexamined Patent Publication No. 6-298817 can be expected to reduce volatile components because it does not contain a photopolymerization initiator. However, a large amount of ultraviolet irradiation is required, and sufficient characteristics cannot be obtained in the obtained cured coating film.

Contents of the invention

The problem to be solved by the invention

The object of the present invention is to provide an alkali-developing type photocurable and thermosetting resin composition, which contains maleimide derivatives, because it does not use a photopolymerization initiator or uses less than the current amount. The volatile components can be reduced, and in addition, it can be cured with less active energy ray exposure.

Another object of the present invention is to provide a printed circuit board formed by forming a cured product composed of such a photocurable/thermosetting resin composition, such as an interlayer insulating layer, a solder resist layer, an optical waveguide layer, and the like.

means of solving problems

In order to achieve the above object, according to the first aspect of the present invention, there is provided a photocurable and thermosetting resin composition that can be developed by an alkaline aqueous solution, characterized in that the composition contains (A) a carboxyl group-containing photosensitive resin, (B) a maleimide derivative, (C) a compound having two or more epoxy groups and/or oxetanyl groups in one molecule, and (D) a compound having a cyclic ether group or a morpholinyl group ( morpholino group) free radical polymerizable compounds.

In addition, the mixing ratio of each component is not limited to a specific ratio, but it is desirable that a maleimide derivative ( B) is mixed in a ratio of 10 to 60 parts by mass, preferably 30 to 50 parts by mass, and the compound (C) having two or more epoxy groups and/or oxetanyl groups in one molecule is 10 to 100 parts by mass The ratio of the compound (D) that can be radically polymerized is mixed in a ratio of 5 to 50 parts by mass, preferably 15 to 30 parts by mass, and when adding a photopolymerization initiator as needed, it can be mixed in a ratio of 3 parts by mass or less Photopolymerization initiator.

In addition, the photocurable and thermosetting resin composition of the present invention can be used directly in liquid form or in the form of a dry film, and can be effectively used in various fields, especially in interlayer insulation layers of printed circuit boards. , solder resist layer, and the formation of the core layer and cladding layer constituting the optical waveguide can be effectively used.

Therefore, according to the second aspect of the present invention, it is possible to provide a cured product obtained by curing the photocurable/thermosetting resin composition by irradiating active energy rays and/or heating. As a preferred embodiment, there is provided a A printed circuit 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 formed from the photocurable/thermosetting resin composition formed printed circuit boards.

The effect of the invention

According to the photocurable/thermocurable resin composition containing a maleimide derivative of the present invention, by containing a radically polymerizable compound having a cyclic ether group or a morpholino group in the composition (Hereinafter, simply referred to as "radical polymerizable compound") Even without adding a photopolymerization initiator, the photocurability of the composition can be improved. As a result, since a photopolymerization initiator is not used or used in a smaller amount than conventionally used, it is possible to provide a resin composition in which volatilized components are reduced during curing or use under high temperature or reduced pressure.

In addition, according to the photocurable/thermosetting resin composition of the present invention, a cured product having excellent alkali developability and adhesion to substrates, electroless plating resistance, electrical insulation, and the like can be obtained.

Therefore, the photocurable/thermosetting resin composition of the present invention is useful as paint, printing ink, adhesive, various resist materials, materials for color filter production, materials for optical waveguides, etc., and is particularly suitable for Solder resists for printed circuit boards, interlayer insulating layers for multilayer printed circuit boards, optical waveguide layers, etc.

In particular, the photocurable/thermosetting resin composition of the present invention, which can be cured without a photopolymerization initiator, can suppress light scattering caused by photopolymerization initiator particles and light absorption caused by the photopolymerization initiator. The loss of light is beneficial to the formation of optical waveguides with excellent light propagation properties.

Description of drawings

Fig. 1 is a partial sectional view of an example of a multilayer printed circuit board.

Fig. 2 is a partial sectional view of an example of an optical waveguide.

Symbol Description

1: Circuit board, 2: Conductor layer, 3: Insulating resin layer, 4: Via hole, 5: Interlayer via hole, 6: Conductor layer, 11: Substrate, 12: Lower cladding, 13: core, 14: upper cladding

Detailed ways

As a result of earnest research by the present inventors in order to solve the above-mentioned problems, it was found that by including a radically polymerizable compound (D) having a specific structure in a photocurable and thermosetting resin composition containing a maleimide derivative, , the photocurability of the composition can be improved without adding a photopolymerization initiator, that is, the composition can be sufficiently cured even with a small amount of active energy ray irradiation, and the present invention has been completed so far. In addition, the photocurable and thermosetting resin composition of the present invention contains these maleimide derivatives (B) and a compound (D) that can be radically polymerized, and contains a carboxyl group-containing photosensitive resin (A) and a The compound (C) having two or more epoxy groups and/or oxetanyl groups in the molecule can be developed with a dilute alkaline aqueous solution, and its cured coating film also has adhesion, electroless plating resistance, A cured coating film with excellent electrical properties, etc.

Hereinafter, each component of the photocurable/thermosetting resin composition of this invention is demonstrated.

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 can be used as long as it has an unsaturated group and a carboxyl group, and it is not limited to a specific one. Among them, the following resins are preferable.

(1) A carboxyl group-containing photosensitive resin obtained by adding an ethylenically unsaturated group as a side group to a copolymer of an unsaturated carboxylic acid and a compound having an unsaturated double bond.

(2) make the compound with epoxy group and unsaturated double bond and the copolymer with the compound of unsaturated double bond react with unsaturated carboxylic acid, then make the generated secondary hydroxyl react with polybasic acid anhydride, thus obtain Carboxyl-containing photosensitive resin.

(3) A carboxyl group-containing photosensitive resin 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.

(4) A carboxyl group-containing photosensitive resin obtained by reacting a polyfunctional epoxy compound with an unsaturated monocarboxylic acid, and then reacting the generated secondary hydroxyl group with a polybasic acid anhydride.

(5) A carboxyl group-containing resin is obtained by reacting a hydroxyl group-containing polymer with a polybasic acid anhydride, and then reacting the resin with a compound having an epoxy group and an unsaturated double bond to obtain a carboxyl group-containing photosensitive resin.

(6) react the polyfunctional oxetane compound with an unsaturated monocarboxylic acid, and then react the primary hydroxyl group in the obtained modified oxetane resin with a polybasic anhydride to obtain a carboxyl-containing photosensitive Sexual resin.

The above carboxyl group-containing photosensitive resins may be used alone or in combination of two or more.

Next, as the maleimide derivative (B) used in the present invention, there are:

(B-1) monofunctional aliphatic/alicyclic maleimide,

(B-2) monofunctional aromatic maleimide,

(B-3) multifunctional aliphatic/alicyclic maleimide,

(B-4) Multifunctional aromatic maleimide.

As the monofunctional aliphatic/alicyclic maleimide (B-1), for example, N-methylmaleimide, N-ethylmaleimide, JP 11-302278 The reactants of maleimide carboxylic acid and tetrahydrofurfuryl alcohol disclosed in No.

As a monofunctional aromatic maleimide (B-2), N-phenyl maleimide, N-(2-methylphenyl) maleimide, etc. are mentioned, for example.

Examples of the polyfunctional aliphatic/alicyclic maleimide (B-3) include N,N'-methylenebismaleimide, N,N'-ethylenebismaleimide Maleimide ester compounds in which imides, tris(hydroxyethyl)isocyanurates and aliphatic/alicyclic maleimide carboxylic acids undergo dehydration esterification to obtain an isocyanurate skeleton, Maleimide urethane compounds with isocyanurate skeleton obtained by urethanation of tris(urethanehexyl)isocyanurate and aliphatic/alicyclic maleimide alcohol, etc. Isocyanurate skeleton polymaleimides, isophorone diurethane bis(N-ethylmaleimide), triethylene glycol bis(maleimide ethyl carbonate), Dehydration esterification of aliphatic/alicyclic maleimide carboxylic acid with various aliphatic/alicyclic polyols, or aliphatic/alicyclic maleimide carboxylic acid esters with various aliphatic/aliphatic Aliphatic/alicyclic polymaleimide ester compounds obtained by transesterification of alicyclic polyols, aliphatic/alicyclic maleimide carboxylic acids and various aliphatic/alicyclic Aliphatic/alicyclic polymaleimide ester compounds obtained by the ether ring-opening reaction of polyepoxides, aliphatic/alicyclic maleimide alcohols and various aliphatic/alicyclic polyamides Aliphatic/alicyclic polymaleimide urethane compounds obtained by urethane reaction of isocyanate, etc.

As polyfunctional aromatic maleimide (B-4), for example, N, N'-(4,4'-diphenylmethane) bismaleimide, N, N'-(4 , 4'-diphenyloxy)bismaleimide, N,N'-p-phenylene bismaleimide, N,N'-m-phenylene bismaleimide, N, Dehydration esterification of N'-2,4-toluene bismaleimide, N,N'-2,6-toluene bismaleimide, maleimide carboxylic acid and various aromatic polyols , or maleimide carboxylic acid esters and various aromatic polyols by transesterification of aromatic polymaleimide ester compounds, maleimide carboxylic acid and various aromatic polycyclic Aromatic polymaleimide ester compounds obtained by ether ring-opening reaction of oxides, aromatic polymaleimide ester compounds obtained by urethane reaction of maleimide alcohol and various aromatic polyisocyanates Aminourethane compounds, etc.

In order to use a monofunctional aliphatic/alicyclic maleimide (B-1) as a monofunctional maleimide in the above-mentioned maleimide derivative (B), a monofunctional aromatic maleimide For imide (B-2), to obtain a cured product with a low exposure amount, it is necessary to use in combination a polyfunctional (meth)acrylate as a diluent described later. In addition, in this 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 will absorb active energy rays, and it is difficult to use it in a product that requires high sensitivity. composition.

On the other hand, polyfunctional aliphatic/alicyclic maleimide (B-3) is preferable because it has high curability and excellent physical properties of a cured coating film after active energy ray irradiation. In particular, a maleimide alkyl carboxylic acid or a maleimide alkyl carboxylate having an alkyl group having 1 to 6 carbon atoms, more preferably a linear alkyl group, and a number average molecular weight of 100 to 100 are combined. 1000 polyethylene glycol and/or polypropylene glycol with a number average molecular weight of 100 to 1000 and/or polytetramethylene glycol with a number average molecular weight of 100 to 1000 undergo dehydration esterification or transesterification reaction to obtain the following general formula (1) and the aliphatic bismaleimide compound represented by the general formula (2) are particularly preferable because the curability of the obtained composition and the balance of the physical properties of the coating film are excellent.

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 resins (A), Preferably it is the ratio of 30-50 mass parts. When the compounding quantity of a maleimide derivative (B) is less than 10 mass parts, sufficient photoreactivity cannot be acquired, and a pattern cannot be formed. On the other hand, when it exceeds 60 mass parts, the developability of a dry coating film will deteriorate.

[chemical 1]

(In the formula, m is an integer of 1 to 6, n is a value of 2 to 23, and ^R1 represents a hydrogen atom or a methyl group.)

[Chem 2]

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

In the photocurable and thermosetting resin composition of the present invention, in order to obtain sufficient physical properties of the cured coating film, a compound (C ), that is, a multifunctional epoxy compound (C-1) and/or a multifunctional oxetane compound (C-2).

As the polyfunctional epoxy compound (C-1), specifically, Epikote828, Epikote834, Epikote1001, Epikote1004 manufactured by Japan Epoxy Resin Co., Ltd., Epiclon840, Epiclon850, Epiclon1050, Epiclon2055 manufactured by Dainippon Ink Chemical Industry Co., Ltd., Epotote YD-011, YD-013, YD-127, YD-128 manufactured by Dongdu Chemical Co., Ltd., D.E.R.317, D.E.R.331, D.E.R.661, D.E.R.664 manufactured by Dow Chemical Company, and Araldite 6071 manufactured by Seba Specialty Chemicals Co., Ltd. , Araldite6084, AralditeGY250, Araldite GY260, SumiepoxyESA-011, ESA-014, ELA-115, ELA-128 manufactured by Sumitomo Chemical Industries, Ltd., A.E.R.330, A.E.R.331, A.E.R.661, A.E.R.664 manufactured by Asahi Kasei Industries, etc. (all Trade name) Bisphenol A type epoxy resin; Epikote YL903 manufactured by Nippon Epoxy Resin Co., Ltd., Epiclon152 and Epiclon165 manufactured by Dainippon Ink Chemical Industry Co., Ltd., Epotote YDB-400 and YDB-500 manufactured by Tohto Kasei Co., Ltd., Dow Chemical D.E.R.542 manufactured by the company, Araldite8011 manufactured by Saiba Specialty Chemicals Co., Ltd., Sumiepoxy ESB-400, ESB-700 manufactured by Sumitomo Chemical Industries, Ltd., A.E.R.711, A.E.R.714 manufactured by Asahi Kasei Industries, etc. (all trade names) brominated Epoxy resin; Epikote 152, Epikote 154 manufactured by Nippon Epoxy Co., Ltd., D.E.N.431, D.E.N.438 manufactured by Dow Chemical Company, Epiclon N-730, Epiclon N-770, Epiclon N- 865, Epotote YDCN-701, YDCN-704 manufactured by Toto Chemical Co., Ltd., Araldite ECN1235, Araldite ECN1273, Araldite ECN1299, Araldite XPY307 manufactured by Seba Specialty Chemicals Co., Ltd., EPPN-201, EOCN-1025, EOCN- manufactured by Nippon Kayaku Corporation 1020, EOCN-104S, RE-306, Sumiepoxy ESCN-195X, ESCN-220 manufactured by Sumitomo Chemical Industries, A.E.R.ECN-235, ECN-299 manufactured by Asahi Kasei Industries, etc. (all Trade name) novolak type epoxy resin; Epiclon830 manufactured by Dainippon Ink Chemical Industry Co., Ltd., Epikote807 manufactured by Nippon Epoxy Resin Co., Ltd., EpototeYDF-170, YDF-175, YDF-2004 manufactured by Tohto Kasei Co., Ltd., Seba special Bisphenol F-type epoxy resins such as Araldite XPY306 (trade names) manufactured by Chemical Co., Ltd.; hydrogenated bisphenol A type such as Epotote ST-2004, ST-2007, ST-3000 (trade names) manufactured by Tohto Chemical Co., Ltd. Epoxy resin: Epikote604 manufactured by Japan Epoxy Resin Co., Ltd., Epotote YH-434 manufactured by Tohto Chemical Co., Ltd., Araldite MY720 manufactured by Seba Specialty Chemicals Corporation, Sumiepoxy ELM-120 manufactured by Sumitomo Chemical Industry Co., Ltd. (all are commercial products) name) glycidylamine-type epoxy resin; hydantoin-type epoxy resin such as Araldite CY-350 (trade name) manufactured by Seba Special Chemicals; Celoxide 2021 manufactured by Daicel Chemical Co., Ltd., Seba Special Chemicals Araldite CY175, CY179, etc. (all trade names) manufactured by the company; YL-933 manufactured by Japan Epoxy Co., Ltd.; T.E.N., EPPN-501, EPPN-502 manufactured by Dow Chemical Company, etc. (all (trade name) trishydroxyphenylmethane type epoxy resin; YL-6056, YX-4000, YL-6121 (all trade names) manufactured by Japan Epoxy Co., Ltd. Resins or their mixtures; bisphenol S-type epoxy resins such as EBPS-200 manufactured by Nippon Kayaku Co., Ltd., EPX-30 manufactured by Asahi Electric Chemical Industry Co., Ltd., and EXA-1514 (trade name) manufactured by Dainippon Ink Chemical Industry Co., Ltd.; Bisphenol A novolac epoxy resins such as Epikote157S (trade name) manufactured by Japan Epoxy Resin Corporation; Epikote YL-931 manufactured by Japan Epoxy Resin Corporation, and Araldite163 manufactured by Seba Specialty Chemicals Corporation (both trade names ) Tetrahydroxyphenylethane type epoxy resin; Araldite PT810 manufactured by Seba Specialty Chemicals Co., Ltd., TEPIC manufactured by Nissan Chemical Industry Co., Ltd. (both trade names) heterocyclic epoxy resin; Blemmer manufactured by NOF Corporation Diglycidyl phthalate resins such as DGT; tetraglycidyl xylenoyl ethane resins such as ZX-1063 manufactured by Tohto Chemical Co., Ltd.; ESN-190 and ESN manufactured by Nippon Steel Chemical Co., Ltd. -360, naphthyl-containing epoxy resins such as HP-4032, EXA-4750, EXA-4700 manufactured by Dainippon Ink Chemical Industry Co., Ltd.; Epoxy resins with a dicyclopentadiene skeleton such as HP-7200 and HP-7200H manufactured by the company; glycidyl methacrylate copolymer epoxy resins such as CP-50S and CP-50M manufactured by NOF Corporation; and There are copolymerized epoxy resins of cyclohexylmaleimide and glycidyl methacrylate, etc., but are not limited to these. These epoxy resins can be used individually or in combination of 2 or more types. Among these, biphenol-type or bixylenol-type epoxy resins or mixtures thereof are particularly preferable.

Furthermore, as a representative example of the polyfunctional oxetane compound (C-2) used in this invention, the compound represented by following General formula (3) or following General formula (13) is mentioned.

[Chem 3]

(In the above general formula (3), ^R is a hydrogen atom or an alkyl group with 1 to 6 carbon atoms, and P is selected from linear or branched saturated hydrocarbons, carbon atoms with 1 to 12 carbon atoms Linear or branched unsaturated hydrocarbons with a number of 2 to 12, aromatic hydrocarbons represented by the following formulas (4), (5), (6), (7) and (8), including formula (9 ) and (10) carbonyl straight-chain or cyclic alkylenes, aromatic hydrocarbons containing carbonyl represented by formulas (11) and (12) have a divalent atomic valence group.)

[chemical 4]

(In the formula, R ³ represents a hydrogen atom, an alkyl, aryl or aralkyl group with 1 to 12 carbon atoms, R ⁴ represents -O-, -S-, -CH ₂ -, -NH-, -SO ₂ -, -CH(CH ₃ )-, -C(CH ₃ ) ₂ - or -C(CF ₃ ) ₂ -, and R ⁵ represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

[chemical 5]

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

[chemical 6]

[chemical 7]

(In the formula, ^R6 is synonymous with the above-mentioned ^R2 , and Q represents a branched chain alkylene group with 3 to 12 carbon atoms comprising the following formula (14), (15), (16) or (17), generally Aromatic hydrocarbons represented by formulas (18), (19) and (20). In addition, l represents the number of functional groups bonded to the residue Q, which is an integer of 3 or more, preferably an integer of 3 to 100.)

[chemical 8]

[chemical 9]

(In the formula, R ⁷ represents a hydrogen atom, an alkyl group or an aryl group with 1 to 6 carbon atoms.)

In addition to the above-mentioned compounds, those obtained by copolymerizing oxetanealcohol and (meth)acrylic acid ester derived from (meth)acrylic acid can also be used. compound.

The above-mentioned oxetane compounds (C-2) 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 can improve characteristics such as adhesiveness and heat resistance of the solder resist by thermosetting. It is sufficient that the compounding quantity is 10 mass parts or more and 100 mass parts or less with respect to 100 mass parts of said carboxyl group-containing photosensitive resins (A), Preferably it is a ratio of 25-60 mass parts. When the mixing amount of the compound (C) having two or more epoxy groups and/or oxetanyl groups in the above-mentioned molecule is less than 10 parts by mass, the crosslinking density of the cured coating film decreases, and soldering becomes easy. Heat resistance or electroless plating resistance is reduced. On the other hand, when it exceeds 100 mass parts, the developability of a dry coating film will deteriorate. Moreover, in order to accelerate the thermosetting reaction of the compound (C) which has 2 or more epoxy groups and/or oxetanyl groups in the said one molecule, the thermosetting catalyst mentioned later can be added.

As the thermal curing catalyst of the compound (C) having two or more epoxy groups and/or oxetanyl groups in one molecule, for example, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-Ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl- 4-methylimidazole and other imidazole derivatives; dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine Amines, amine compounds such as 4-methyl-N,N-dimethylbenzylamine, hydrazine compounds such as adipic hydrazide and sebacic hydrazide, phosphorus compounds such as triphenylphosphine, etc. In addition, commercially available products include, for example, 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, and 2P4MHZ (all are trade names of imidazole compounds) manufactured by Shikoku Chemical Industry Co., Ltd., and U-CAT3503N manufactured by San-Apro Corporation. , U-CAT3502T (all are trade names of blocked isocyanate compounds of dimethylamine), DBU, DBN, U-CATSA102, U-CAT5002 (all are bicyclic amidine compounds and their salts), etc. These are not particularly limited, as long as they are thermosetting catalysts or can accelerate the reaction between epoxy groups or oxetanyl groups and carboxyl groups, they can be used alone or in combination of two or more. In addition, melamine, methylguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl- s-triazine, 2-vinyl-4,6-diamino-s-triazine, 2-vinyl-4,6-diamino-s-triazine·isocyanuric acid adduct, 2,4-diamino -S-triazine derivatives such as 6-methacryloyloxyethyl-s-triazine-isocyanuric acid adduct, it is preferable to combine these compounds that also function as an adhesion imparting agent with the above-mentioned thermosetting catalyst use. The mixing amount of the thermosetting catalyst is sufficient in a usual ratio, for example, 0.1 to 20 parts by mass, preferably 0.5 to 15.0 parts by mass relative to 100 parts by mass of the carboxyl group-containing photosensitive resin (A).

The cyclic ether group in the radically polymerizable compound (D) used in the present invention may, for example, be tetrahydrofuran ring, furan ring, tetrahydropyran ring, 1,3-dioxolane, 1,3 - dioxane, 1,4-dioxane, etc., among which tetrahydrofuran ring is preferred.

Therefore, the radically polymerizable compound (D) used in the present invention is particularly preferably a radically polymerizable compound having a tetrahydrofuran ring or a morpholino group. The detailed reason is not clear, but the light of using these compounds The curable/thermosetting resin composition has very high curability.

In addition, the radically polymerizable compound in the present invention refers to a compound having a radically polymerizable group. Here, radically polymerizable groups refer to groups that undergo radical chain reactions, specifically, (meth)acryloyl groups, (meth)acrylamide groups, (meth)allyl groups, ethylene groups, group, maleimide group, fumaric acid group, itaconic acid group, maleic acid group, etc., especially (meth)acryloyl group has high curability and is effective. In addition, in this specification, (meth)acryloyl, (meth)acrylamide, (meth)allyl refer to acryloyl and/or methacryloyl, acrylamide and/or methacryl respectively Amido, allyl and/or methallyl means.

Thus, by using a radically polymerizable compound having a cyclic ether group or a polymerizable compound having a morpholino group together with the carboxyl group-containing photosensitive resin (A) and the maleimide derivative (B), A compound that is radically polymerized, so that a cured coating film with excellent characteristics can be obtained with a lower amount of ultraviolet irradiation without using a photopolymerization initiator or with a lower amount of photopolymerization initiator than before.

Such a radically polymerizable compound (D) may, for example, be commercially available as TC-110S (trade name) manufactured by Nippon Kayaku Co., Ltd. as tetrahydrofurfuryl alcohol epsilon caprolactam adduct acrylate, or as Tetrahydrofurfuryl acrylate is Biscoat #150 (trade name) manufactured by Osaka Organic Chemical Industry Co., Ltd., or the like.

Furthermore, the radically polymerizable compound (D) can be obtained by, for example, a method (first method) in which the following three components (D-1) to (D-3) are reacted, or the following (D-1 ) is synthesized by reacting the compound of (D-4) (second method).

(D-1) Compounds having a cyclic ether group or a morpholino group and a hydroxyl group,

(D-2) organic polyisocyanates,

(D-3) Compounds having hydroxyl groups and radically polymerizable groups,

(D-4) A compound having an isocyanate group and a radically polymerizable group.

Here, as a compound (D-1) having a cyclic ether group or a morpholino group and a hydroxyl group, for example, tetrahydrofurfuryl alcohol, a mono-ε-caprolactone adduct of tetrahydrofurfuryl alcohol, etc. have Alcohols with a tetrahydrofuran ring.

In addition, alcohols having a tetrahydropyran ring such as tetrahydropyran-2-methanol and a mono-ε-caprolactone adduct of tetrahydropyran-2-methanol may be mentioned.

Further, condensate of 2,2-dimethyl-3-oxopropanal (oxypropanal) and ethylene glycol, condensate of 2,2-dimethyl-3-oxopropanal and ethylene glycol can be exemplified. Dioxolane-containing alcohols such as mono-ε-caprolactone adducts.

In addition, further examples include alcohols having a morpholino group such as morpholino ethanol and 3-morpholino-1,2-propanediol; hydroxyl compounds having a cyclic ether structure; Ether-like amine compounds, etc., but are not limited to these.

As the organic polyisocyanate compound (D-2), for example, aliphatic isocyanates such as trimethylene diisocyanate and hexamethylene diisocyanate; aromatic isocyanates such as m-phenylene diisocyanate and p-phenylene diisocyanate; 2,4 - Modified polyisocyanates such as toluene diisocyanate trimer, hexamethylene diisocyanate trimer, and isophorone diisocyanate trimer; Polyisocyanates obtained by urethane-forming polyhydric alcohols such as trimethylolpropane, etc., but are not limited to these.

As a compound (D-3) which has a hydroxyl group and a radically polymerizable group, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, etc. are mentioned, for example.

In addition, a reaction product of a monoepoxide compound and (meth)acrylic acid, such as 2-hydroxy-3-octyloxypropyl (meth)acrylate, 2-hydroxy-3-lauryloxypropyl (meth)acrylate, Propyl ester etc.

Further, the reactant of multifunctional epoxy compound and (meth)acrylic acid or (meth)acrylic acid dimer (for more than 2 epoxy groups of multifunctional epoxy compound, respectively react (meth)acrylic acid or (meth)acrylic acid dimer base) acrylic acid dimer, that is, a compound obtained by reacting 1 mole of a polyfunctional epoxy compound with 2 moles or more of (meth)acrylic acid or (meth)acrylic acid dimer), for example For example, bisphenol A diglycidyl ether/(meth)acrylic acid=1/2 (mol) reactant, bisphenol F diglycidyl ether/(meth)acrylic acid=1/2 (mol) reactant, etc. The above-mentioned compound is an adduct of (meth)acrylic acid, and a compound obtained by adding (meth)acrylic acid dimer to an epoxy compound can also be used.

In addition, the compound (D-3) having a hydroxyl group and a radically polymerizable group is not limited to the compounds exemplified here.

As the compound (D-4) having an isocyanate group and a radically polymerizable group, for example, methacrylic acid isocyanate, 2-methacryloyloxyethyl isocyanate, etc. and (meth)acrylic acid 2-hydroxyethyl 1:1 addition reaction product of (meth)acrylate having a hydroxyl group, such as ester, 2-hydroxypropyl (meth)acrylate, etc.

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

Compound (D-1) with cyclic ether group or morpholino group (morpholino group) and hydroxyl group and organic polyisocyanate (D-2) and compound (D-3) with hydroxyl group and free radical polymerizable group Reaction (the 1st method), and the reaction (the 2nd method) of above-mentioned compound (D-1) and the compound (D-4) that has isocyanate group and radically polymerizable group, not specifically limited, can be by known Synthesized by urethane reaction.

These reactions are carried out in a nitrogen atmosphere, for example, at a temperature range from room temperature to 90° C., preferably using a catalyst. In the first method above, the compound (D-1) having a cyclic ether group or a morpholino group and a hydroxyl group and a compound (D-1) having a hydroxyl group and a free The sum of the hydroxyl groups of the polymerized group compound (D-3) is desirably 0.9 to 1.2 equivalents, preferably 1.0 to 1.1 equivalents.

In addition, in the second method, the compound having a cyclic ether group or a morpholino group and a hydroxyl group is equivalent to 1 equivalent of the isocyanate group of the compound (D-4) having an isocyanate group and a radically polymerizable group The hydroxyl group in (D-1) is desirably 0.9 to 1.2 equivalents, preferably 1.0 to 1.1 equivalents.

As the catalyst used for the above-mentioned addition reaction of hydroxyl group and isocyanate, for example, organic titanium compounds such as tetrabutyl titanate, tetrapropyl titanate, tetraethyl titanate, tin octoate, dibutyltin oxide, dibutyltin oxide, etc., can be used. Organotin compounds such as dibutyltin laurate, stannous iodide, etc. The addition amount of the catalyst is preferably in the range of 10 to 10000 ppm with respect to the entire feed amount.

In addition, a compound having a radically polymerizable group that does not contain active hydrogen such as hydroxyl group, amino group, or mercapto group, and/or an organic solvent that does not contain active hydrogen such as hydroxyl group, amino group, or mercapto group can be used as the reaction solvent. Examples of organic solvents include aromatic hydrocarbons such as toluene, ethylbenzene, 1,2,3,4-tetralin, cumene, and xylene; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexane Ketones such as ketones; esters such as formate, methyl acetate, ethyl acetate, and n-butyl acetate, but are not limited to these.

In addition, in any of the above reactions, it is desirable to use a radical polymerization inhibitor in order to suppress the polymerization of the radical polymerizable group. As a radical polymerization inhibitor, for example, hydroquinone, tert-butylhydroquinone, hydroquinone methyl ether (methoquinone), 2,4-dimethyl-6-tert-butylphenol, catechol, tert-butyl Phenolic compounds such as tea phenol; amines such as phenothiazine, p-phenylenediamine, and diphenylamine; copper dimethyldithiocarbamate, copper diethyldithiocarbamate, dibutyldithiocarbamate Copper complexes such as copper urethane, etc. These polymerization inhibitors may be used alone or in combination of two or more. It is preferable that the addition amount of a polymerization inhibitor is the range of 10-10000 ppm with respect to the whole charge amount.

Containing the above-mentioned carboxyl group-containing photosensitive resin (A), a maleimide derivative (B), a compound (C) having two or more epoxy groups and/or oxetanyl groups in one molecule, and free In the photocurable/thermocurable resin composition of the present invention, in which the compound (D) polymerized by radical polymerization is an essential component, it is not necessary to add a photopolymerization initiator, but when it is necessary to cure with a lower exposure amount, in In the range which does not impair the effect of this invention, a photoinitiator can be mixed as needed to improve photocurability.

As the photopolymerization initiator, for example, 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-2-phenylacetophenone, 1,1-dichloroacetophenone and other acetophenones; 2-methyl-1-[4-(methylthio)phenyl]-2 -Morpholinoamino-1-propanone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butane-1-one, N,N-dimethylaminoacetophenone Isoaminoacetophenones, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone and other anthraquinones; 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone and other thioxanthones; acetophenone dimethyl ketal, benzyl dimethyl acetal Ketals such as ketones; organic peroxides such as benzoyl peroxide and cumene peroxide; 2,4,5-triaryl imidazole dimers; riboflavin tetrabutyrate; 2-mercaptobenzimidazole , 2-mercaptobenzoxazole, 2-mercaptobenzothiazole and other thiol compounds; 2,4,6-tri-s-triazine; 2,2,2-tribromoethanol, tribromomethylphenyl sulfone, etc. Organic halogen compounds; benzophenones such as benzophenone and 4,4'-bisdiethylaminobenzophenone or xanthones; 2,4,6-trimethylbenzoyldiphenyl phosphine oxides; oximes such as 2-(acetoxyiminomethyl)thioxanthen-9-one, etc. These well-known and commonly used photopolymerization initiators can be used alone or as a mixture of two or more, and photoinitiator auxiliaries can be added, such as N,N-dimethylaminobenzoic acid ethyl ester, N,N-dimethylaminobenzene Tertiary amines such as isoamyl formate, pentyl-4-dimethylaminobenzoate, triethylamine, triethanolamine, etc. In addition, in order to promote the photoreaction, a titanocene compound such as CGI-784 (manufactured by Seba Specialty Chemicals Co., Ltd.) which absorbs in the visible region may be added. Particularly preferred photopolymerization initiators are 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinoamino-1-propanone, 2-benzyl-2-dimethylamino- 1-(4-morpholinophenyl)-butan-1-one, 2-(acetoxyiminomethyl)thioxanth-9-one, etc., but not particularly limited to these, as long as it is UV Light or visible light absorbs light to cause free radical polymerization of unsaturated groups such as (meth)acryloyl groups, and is not limited to photopolymerization initiators and photoinitiator assistants, which can be used alone or in combination. Furthermore, when an oxime-based photopolymerization initiator such as the above-mentioned 2-(acetoxyiminomethyl)thioxanth-9-one is used, since the sensitivity is high, laser direct imaging technology can be applied.

The compounding amount of the photopolymerization initiator (when a photoinitiator auxiliary agent is used is their total amount) is preferably 3 parts by mass or less, more preferably A ratio of 2 parts by mass or less. When the quantity of the photoinitiator to mix is more than the said range, the quantity of a volatile component will increase, and the effect of this invention will be impaired.

In the photocurable/thermosetting resin composition of the present invention, a diluent consisting of a photopolymerizable monomer and/or an organic solvent may be mixed as necessary. The purpose of using the diluent is: in the case of a photopolymerizable monomer, dilute the photosensitive component to make it easy to coat, and enhance the photopolymerization; on the other hand, in the case of an organic solvent, by dissolving and diluting the photosensitive component Components are made into a liquid state that is easy to apply, and film formation is performed by drying, making contact exposure possible. Therefore, depending on the diluent to be used, either a contact method or a non-contact method for bringing the photomask into close contact with the coating film can be used.

Further, as the maleimide derivative (B), when using a monofunctional aliphatic/alicyclic maleimide (B-1) or a monofunctional aromatic maleimide (B-2) In the case, as described above, since it is difficult to increase the sensitivity, a photopolymerizable monomer is used as a diluent.

Typical examples of photopolymerizable monomers include hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate; ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, Mono- or diacrylates of diols such as alcohol and propylene glycol; acrylamides such as N,N-dimethylacrylamide, N-methylolacrylamide, N,N-dimethylaminopropylacrylamide; acrylic acid N , N-dimethylaminoethyl ester, N, N-dimethylaminopropyl acrylate and other aminoalkyl acrylates; hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, trihydroxyethylisocyanurate Polyhydric alcohols such as acid esters or polyacrylic acid esters such as ethylene oxide adducts or propylene oxide adducts; phenoxy acrylate, bisphenol A diacrylate, and ethylene oxide of these phenols Acrylic esters such as alkylene adducts or propylene oxide adducts; Acrylic esters of glycerin ether; and melamine acrylate, and/or respective methacrylates corresponding to the above-mentioned acrylates; and the like.

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 ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether and other glycol ethers; ethyl acetate, butyl acetate and the above two Esters such as acetate esters of alcohol ethers; alcohols such as ethanol, propanol, ethylene glycol, propylene glycol, etc.; aliphatic hydrocarbons such as octane, decane, etc.; petroleum ether, naphtha, hydrogenated naphtha, solvent stone Petroleum solvents such as naphtha, etc.

Such diluents may be used alone or as a mixture of two or more. When using a photopolymerizable monomer, it is desirable to use an appropriate amount in the range of 100 parts by mass of the carboxyl group-containing photosensitive resin (A). 10 to 60 parts by mass, preferably 15 to 50 parts by mass, and when the amount used is more than this range, the dryness to the touch of the dried coating film deteriorates, which is not preferable. On the other hand, the amount of the organic solvent used is not limited to a specific ratio, but it is suitable to be in the range of about 30 to 300 parts by mass with respect to 100 parts by mass of the carboxyl group-containing photosensitive resin (A). Appropriately set the coating method.

In addition, in the photocurable/thermosetting resin composition of the present invention, in order to reduce the dielectric constant and dielectric loss tangent of its cured product according to the application, and not to cause their applicability or heat resistance, etc. The characteristics are lowered, and spherical porous fillers can be mixed. The material of the spherical porous filler may, for example, be silica or a cross-linked resin.

When a general filler is mixed with a photocurable/thermosetting resin composition, it is governed by the dielectric constant and dielectric loss tangent of the cured product, but when a spherical porous filler is mixed, the pores contain air , thus reducing its dielectric properties. In order to contain air in this way, the average particle size of the spherical porous filler is preferably 1 to 15 μm, more preferably in the range of 1 to 10 μm, and the oil absorption of the spherical porous filler is preferably about 100 to 500 ml. /100g, preferably 150-300ml/100g.

The mixing ratio of such a spherical porous filler is preferably 5 parts by mass or more and 100 parts by mass or less, preferably 50 parts by mass or less, with respect to 100 parts by mass of the above-mentioned carboxyl group-containing photosensitive resin (A).

In the photocurable/thermosetting resin composition of the present invention, epoxidized polybutadiene and spherical polyurethane beads may be mixed as necessary within the range not impairing the effect of the present invention.

Epoxidized polybutadiene is blended to impart flexibility and strength. As the epoxidized polybutadiene, there are, for example, Epolead PB3600 and PB4700 manufactured by Daicel Chemical Industry Co., Ltd., and the mixing amount thereof is preferably 5 to 50 parts by mass relative to 100 parts by mass of the above-mentioned carboxyl group-containing photosensitive resin (A). .

Spherical polyurethane beads are mixed with an average particle diameter of 1 to 15 μm in order to impart flexibility and low warpage. The compounding quantity of this spherical polyurethane bead is desirably 5-100 mass parts with respect to 100 mass parts of said carboxyl group containing photosensitive resins (A).

In the photocurable/thermosetting resin composition of the present invention, barium sulfate, barium titanate, silica powder, finely powdered silica, and amorphous silica may be mixed individually or in combination of two or more types as required. , crystalline silica, fused silica, spherical silica, talc, clay, magnesium carbonate, calcium carbonate, alumina, aluminum hydroxide, mica and other well-known and commonly used inorganic fillers. These inorganic fillers are used to suppress curing shrinkage of the coating film and to improve characteristics such as adhesion and hardness. The compounding quantity of an inorganic filler is 10-300 mass parts with respect to 100 mass parts of said carboxyl group containing photosensitive resins (A), Preferably it is 30-200 mass parts.

The photocurable and thermosetting resin composition of the present invention can also be mixed with known and commonly used additives as required, such as phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow, crystal violet, titanium oxide, carbon black , naphthalene black and other well-known and commonly used colorants, hydroquinone, hydroquinone monomethyl ether, tert-butyl catechol, pyrogallol, phenothiazine and other well-known and commonly used thermal polymerization inhibitors, micronized silica, organic bentonite , montmorillonite and other well-known and commonly used thickeners, silicone, fluorine, polymer and other defoamers and/or leveling agents, imidazoles, thiazoles, triazoles and other silane coupling agents, etc. .

The photocurable/thermosetting resin composition of the present invention can be obtained by mixing the above-mentioned mixing components preferably in the above ratios, uniformly mixing, dissolving, dispersing, etc. with a roll mill or the like. The resin composition is usually in liquid form, but it can also be made into a dry film.

When making a dry film, it can be obtained through the following procedures: for example, using a roll coater or a scraper, a wire rod method, a dip coating method, a spin coating method, a gravure printing method and a doctor blade method, etc., to apply the photocurable After the thermosetting resin composition is coated on the base film (release film), it is dried in a drying oven set at about 60 to 100° C., and a release film or the like is attached as necessary. At this time, the thickness of the dried coating film on the base film is adjusted to 5 to 160 μm, preferably 10 to 60 μm. As the base film, films such as polyethylene terephthalate and polypropylene can be suitably used.

The photocurable and thermosetting resin composition of the present invention having the above composition is diluted as necessary, adjusted to a viscosity suitable for the coating method, and is applied by screen printing, curtain coating, spray coating, or roll coating. Appropriate methods such as method, spin coating method, etc., apply it to a printed circuit board formed with a circuit, and evaporate and dry the organic solvent contained in the composition at a temperature of about 60 to 100°C, thereby forming a coating. membrane. Thereafter, through a photomask formed with a pattern, selective exposure is performed with active energy rays, and the unexposed part is developed with a dilute alkaline aqueous solution to form a photoresist pattern. Curing or heat curing followed by active energy ray irradiation, or final curing (full curing) by heat curing alone, can form a cured film (solder resist film) excellent in adhesion, electroless plating resistance, and electrical properties .

As the alkaline aqueous solution, alkaline aqueous solutions of potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, amines and the like can be used.

In addition, as an 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 suitable. In addition, laser light or the like can also be used as the active energy ray.

In addition, when using the photocurable/thermosetting resin composition of the present invention to form an interlayer insulating resin layer of a multilayer printed wiring board, the viscosity is adjusted to a suitable coating method as necessary, and by the above-mentioned conventionally known method, For example, as shown in FIG. 1, it is coated on the conductor layer 2 of the circuit board 1 on which the circuit is formed in advance, and dried at a temperature of about 60 to 100°C as needed to form a coating film that is dry to the touch, and then passed A negative having opaque portions of a predetermined shape such as black circles is selectively exposed with active energy rays, and the unexposed portions are developed with an alkaline aqueous solution such as the above to form via holes 4 corresponding to the black circles of the negative. Thereafter, if necessary, perform prescribed interlayer via holes 5, etc., and then use a roughening agent such as an oxidizing agent, an alkaline aqueous solution, or an organic solvent to perform surface roughening treatment, and the roughened insulating resin layer 3 surface The conductive layer is covered by electroless plating, electroplating, etc., and then heat treatment is performed to increase the cross-linking density of the above-mentioned insulating resin layer 3 and perform stress relaxation. By heating and curing at a temperature of, for example, about 140 to 180° C., an interlayer insulating resin layer 3 excellent in various characteristics such as adhesion, electroless plating resistance, and electrical characteristics can be formed. Thereafter, the conductor layer on the surface of the insulating resin layer 3 is etched according to a conventional method to form a predetermined circuit pattern, and the circuit-formed conductor layer 6 is formed. In addition, these operations may be repeated sequentially as required to alternately build up the insulating resin layer and the conductor layer of the predetermined circuit pattern.

In addition, the photocurable and thermosetting resin composition of the present invention can be used not only as an insulating resin layer in a multilayer printed circuit board manufacturing method by the above-mentioned build up method, but also in, for example, a It is used to form an insulating resin layer in the production of multilayer printed circuit boards by the copper foil lamination method, or as an insulating resin composition for prepregs used in the laminate press method, etc.

On the other hand, the photocurable/thermosetting resin composition of the present invention can be used for forming a core layer or a clad layer of an optical waveguide.

An 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 an optical waveguide. For example, the photocurable and thermosetting resin composition for cladding is adjusted to a viscosity suitable for the coating method as needed, and is coated on a substrate 11 such as a silicon wafer by a conventionally known method. Dry at 100°C to volatilize the organic solvent, then irradiate active energy rays from above to expose, and then heat and cure in a hot air circulation drying oven at about 140 to 180°C to form the lower cladding layer for optical waveguides 12. On it, apply a photocurable and thermosetting resin composition for the core layer with a higher refractive index than the above composition, dry it at a temperature of about 60 to 100°C, volatilize the organic solvent, and then see through it from above. The core layer 13 is formed by irradiating active energy rays through the negative film for selective exposure, then developing the unexposed part with an alkaline aqueous solution, and then performing thermal curing in a hot air circulation drying oven at about 140-180°C. Thereafter, the photocurable and thermosetting resin composition for the cladding layer is applied on the core layer 13, dried at a temperature of about 60 to 100° C. to evaporate the organic solvent, and then irradiated with active energy from above. The upper cladding layer 14 is formed by exposing to radiation, followed by thermal curing in a hot air circulating drying oven at about 140° C. to 180° C. In this way, a multi-model optical waveguide can be fabricated.

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 also be adjusted by a method of adjusting the polarization of the bonding segment by changing the reaction system, or by changing the structure of the compound to adjust the refractive index of the molecule. In a system containing a carboxyl group-containing photosensitive resin (A) as an essential component such as the photocurable/thermosetting resin composition of the present invention, compared with the means for adjusting the amount of reactive groups, by changing the main skeleton of the resin or by changing Adjusting the refractive index by means of adjusting the mixing ratio is easier and more effective.

In order to increase the refractive index of organic compounds, it is effective to increase the molecular refraction or reduce the molecular volume. Specifically, introduction of conjugated structures such as benzene rings, sulfur, -COO-, -COOH, SO ₂ , CS, fluorine, etc. The introduction of halogen atoms is effective, but the introduction of bromine or chlorine is not preferable from the viewpoint of environmental load. On the other hand, in order to lower the refractive index of organic compounds, it is effective to reduce the molecular refraction or increase the molecular volume. Specifically, introducing an aliphatic ring having 3 to 6 carbon atoms, -OH, -O-, - C=C-, NH ₂ , and fluorine are effective, but polymers containing fluorine have problems in disposal and increase material costs, so the introduction of fluorine is not preferable.

However, in a multimode waveguide, the wider the core width or the larger the difference in refractive index between the core layer and the cladding layer, the more the number of modes and the higher the propagation of light. Usually the difference in refractive index is obtained by ( _n 1-n ₀ )/n ₁ ×100(%) (wherein, n ₁ represents the refractive index of the core layer, and n ₀ represents the refractive index of the cladding layer.) To obtain, in multimode In the waveguide, the refractive index difference is preferably 0.5% or more, more preferably 1.0% or more.

In addition, the size of the core layer changes depending on the difference between the refractive index of the core layer and the cladding layer and the desired mode number. However, when the optical waveguide is used for multi-mode using a communication wavelength near 0.85 μm, the ideal core layer size is In the range of about 20-80 μm. In addition, the presence of large particles in the core layer is not preferable because light scattering loss occurs, and it is generally preferable not to contain particles with a diameter of about 1 μm or more.

A printed circuit board on which an optical waveguide is formed is described in, for example, Japanese Patent Application Laid-Open No. 6-258537 or International Publication WO2004/095093A1, and the inspirations thereof are incorporated herein by reference.

Example

The present invention will be specifically described below with examples and comparative examples, but the present invention is of course not limited to the following examples. In addition, the following "parts" and "%" are mass standards unless otherwise stated.

Synthesis of carboxyl-containing photosensitive resin (A-1):

330 parts of cresol novolac type epoxy resins (Epiclon N-695, manufactured by Dainippon Ink Chemical Industry Co., Ltd., epoxy equivalent 220) are packed into a flask equipped with a gas introduction tube, a stirring device, a cooling tube and a thermometer, and 400 parts are added. Parts of carbitol acetate, heat to dissolve, add 0.46 parts of hydroquinone and 1.38 parts of triphenylphosphine. The mixture was heated to 95-105°C, 108 parts of acrylic acid was slowly added dropwise, and reacted for 16 hours. This reaction product was cooled to 80-90 degreeC, 163 parts of tetrahydrophthalic anhydrides were added, and it was made to react for 8 hours. The reaction is to measure the acid value and total acid value of the reaction solution by potentiometric titration, track the obtained addition rate, and take the reaction rate above 95% as the end point. The carboxyl group-containing photosensitive resin obtained in this way had a non-volatile content of 60%, and an acid value of solid matter of 100 mgKOH/g. Hereinafter, this reaction solution is called varnish A-1.

Synthesis of carboxyl-containing photosensitive resin (A-2):

With 322 parts of phenol novolac type epoxy resins (EPPN-201, Nippon Kayaku Co., Ltd. manufacture, epoxy equivalent 190), pack in the flask that is equipped with gas introduction tube, stirring device, cooling tube and thermometer, add 400 parts of carbites Alcohol acetate, heat to dissolve, add 0.46 parts of hydroquinone and 1.38 parts of triphenylphosphine. The mixture was heated to 95-105°C, 122 parts of acrylic acid was slowly added dropwise, and reacted for 16 hours. This reaction product was cooled to 80-90 degreeC, 156 parts of tetrahydrophthalic anhydrides were added, and it was made to react for 8 hours. The reaction is to measure the acid value and total acid value of the reaction solution by potentiometric titration, track the obtained addition rate, and take the reaction rate above 95% as the end point. The carboxyl group-containing photosensitive resin thus obtained had a non-volatile content of 60%, and an acid value of solid matter of 96 mgKOH/g. Hereinafter, this reaction solution is called varnish A-2.

Synthesis of carboxyl-containing photosensitive resin (A-3):

After 350 parts of bisphenol A type epoxy resins (manufactured by Japan Epoxy Resin Co., Ltd., Epikote1004, epoxy equivalent: 917) and 925 parts of epichlorohydrin were dissolved in 463 parts of dimethyl sulfoxide, under stirring, 61 parts of 99% sodium hydroxide are added within 100 minutes at 70°C. After addition, it was made to react at 70 degreeC for 3 hours, and 250 parts of water were added and washed with water after completion|finish of reaction. After separating the oil, under reduced pressure, recover most of the dimethyl sulfoxide and excess unreacted epichlorohydrin from the oil layer, and dissolve the reaction product containing the residual by-product salt and dimethyl sulfoxide in 750 Parts of methyl isobutyl ketone, and then add 10 parts of 30% NaOH, and react at 70°C for 2 hours. After the reaction was completed, wash twice with 200 parts of water and carry out oil separation, then reclaim methyl isobutyl ketone from the oil layer fractionation to obtain an epoxy resin with an epoxy equivalent of 318. In the obtained epoxy resin, if calculated from the epoxy equivalent, 4.8 of the 5.3 alcoholic hydroxyl groups in the starting material bisphenol A type epoxy resin are epoxidized. 318 parts of this epoxy resin and 351 parts of carbitol acetate were put into a flask, heated and stirred to 90 degreeC, and dissolved. 0.4 parts of methylhydroquinone, 72 parts of acrylic acid, and 4 parts of triphenylphosphine were added to this solution, and it was made to react at 90-95 degreeC for 36 hours, and the reaction product whose acid value was 2.2 mgKOH/g was obtained. After cooling this reaction solution to room temperature, 137 parts of tetrahydrophthalic anhydrides were added, and it heated at 85 degreeC and was made to react. The carboxyl group-containing photosensitive resin thus obtained had a non-volatile content of 60%, and a solid content acid value of 96 mgKOH/g. Hereinafter, this reaction solution is called varnish A-3.

Examples 1-4 and Comparative Examples 1-3

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

Table 1

Table 2

In addition, the method of the performance test in the above-mentioned Table 2 is as follows.

(1) Sensitivity

On the glass epoxy substrate, the compositions of the above-mentioned examples and comparative examples are fully coated with screen printing, dried at 80° C. for 20 minutes, left to cool to room temperature, and then using a staged exposure meter No.2 manufactured by Kodak ( 21 paragraphs) as a photomask, use an exposure device (metal halide lamp 7KW2 lamp) manufactured by Oak Manufacturing Co., Ltd. under reduced pressure to expose with an integrated light meter of 365nm ultraviolet light at 500, 700 or 900mJ/ ^cm2 . Under the condition of a pressure of 0.2 MPa, it was developed with a 1% Na ₂ CO ₃ aqueous solution at 30° C. for 60 seconds, and the number of glossy segments of the cured coating film was visually confirmed. In addition, a larger numerical value indicates a higher sensitivity.

(2) Electrical insulation

On a comb-shaped electrode with L/S=50 μm, use a roll coater manufactured by Pilot Seiko Co., Ltd. to fully coat the compositions of the above-mentioned examples and comparative examples, and then dry them at 80° C. for 30 minutes in a hot air circulation drying oven. minute. After it was cooled to room temperature, Examples 1-4 were exposed under the condition that the exposure amount was 700mJ/cm ² , and Comparative Examples 1-3 were respectively exposed under the condition that the exposure amount was 900, 900, and 500mJ/cm ² . Curing was carried out at 150° C. for 60 minutes in a circulating drying oven to obtain evaluation samples. A bias voltage of DC5.5V was applied to the comb-shaped electrode, and the insulation resistance value was measured after standing at a humidity of 85% and a temperature of 130° C. for 150 hours.

(3) Resistance to electroless gold plating

On the printed circuit board, the compositions of the above-mentioned examples and comparative examples were coated by screen printing, and then dried at 80° C. for 30 minutes in a hot air circulation drying oven. After it was cooled to room temperature, Examples 1-4 were exposed under the condition that the exposure amount was 700mJ/cm ² , and Comparative Examples 1-3 were respectively exposed under the condition that the exposure amount was 900, 900, and 500mJ/cm ² . Curing was carried out at 150° C. for 60 minutes in a circulating drying oven to obtain evaluation samples. The obtained evaluation sample was immersed in an acidic degreasing solution (manufactured by Mac Diarmid, Japan, 20 vol% aqueous solution of METEX L-5B) at 30° C. for 3 minutes, washed with water, and then immersed in a 14.4 wt % ammonium persulfate aqueous solution at room temperature for 3 minutes. After washing with water, immerse in 10vol% sulfuric acid aqueous solution for 1 minute at room temperature. Next, the evaluation substrate was immersed in a catalyst solution (manufactured by Meltex Inc., 10 vol% aqueous solution of metal plate activator 350) at 30°C for 5 minutes, washed with water, and nickel plating solution (manufactured by Meltex Inc., Melplate Ni -865M (20 vol% aqueous solution, pH=4.6) was immersed for 30 minutes to perform nickel plating, and then immersed in 10 vol% sulfuric acid aqueous solution at room temperature for 1 minute to perform water washing. Next, the evaluation sample substrate was immersed in a gold plating solution (manufactured by Meltex Inc., 15 vol% of Aurorectroles UP and 3 vol% aqueous solution of potassium gold cyanide, pH=6) at 95° C. for 30 minutes to perform electroless gold plating, After washing with water, it was immersed in warm water of 60° C. for 3 minutes, and washed with running water. A cellophane adhesive tape was attached to the obtained evaluation sample subjected to gold plating, and the state of the cured coating film at the time of peeling was confirmed. The judgment criteria are as follows.

◯: There is no abnormality in the cured coating film.

Δ: Slight peeling of the cured coating film occurred.

x: The cured coating film peeled off.

From the results of Examples 1 to 4 shown in Table 2, it can be seen that the cured product obtained from the photocurable and thermosetting resin composition of the present invention exhibits good sensitivity, electrical insulation resistance, and durability without using a photopolymerization initiator. Electroless gold plating properties are also excellent.

In contrast, in Comparative Examples 1 and 2, sufficient sensitivity could not be obtained, and the electrical insulation resistance and electroless gold plating resistance of the obtained cured products deteriorated. In addition, in Comparative Example 3 using a photopolymerization initiator, a decrease in insulation resistance due to bleeding of the photopolymerization initiator was observed.

Industrial use field

The photocurable and thermosetting resin composition of the present invention is used as various coating materials such as paints, printing inks, surface treatment agents, molding materials, adhesives, adhesives, adhesives, various resist materials, filters, etc. Materials for color chip production, materials for optical waveguides, and the like are useful, and are particularly useful in forming solder resists for printed wiring boards, interlayer insulating layers, optical waveguide layers, and the like in multilayer printed wiring boards.

Claims (8)

1. A photocurable and thermosetting resin composition capable of being developed by an alkaline aqueous solution, characterized in that the composition contains (A) a carboxyl group-containing photosensitive resin having an unsaturated group and a carboxyl group, (B) Selected from (B-1) monofunctional aliphatic/alicyclic maleimide, (B-2) monofunctional aromatic maleimide, (B-3) multifunctional aliphatic/alicyclic maleimide Maleimides, (B-4) maleimide derivatives in the group consisting of polyfunctional aromatic maleimides, (C) having two or more epoxy groups and/or oxygen groups in one molecule A heterocyclobutanyl compound, and (D) an acryloyl or methacryloyl compound having a cyclic ether group or a morpholinyl group, 10 to 60 parts by mass of the maleimide derivative (B), 10 to 100 parts by mass of A compound (C) having two or more epoxy groups and/or oxetanyl groups, and 5 to 50 parts by mass of the acryloyl or methacryloyl compound (D). 2. The photocurable and thermosetting resin composition according to claim 1, wherein the cyclic ether group of the acryloyl or methacryloyl compound (D) having a cyclic ether group or a morpholino group is Tetrahydrofuran ring. 3. The photocurable and thermosetting resin composition according to claim 1, wherein the carboxyl group-containing photosensitive resin (A) is 1 selected from the group consisting of the following (1) to (6). 2 or more types: (1) On the copolymer of unsaturated carboxylic acid and compound having unsaturated double bonds, add ethylenically unsaturated groups as side groups, thus obtained carboxyl-containing photosensitive resin; (2) make the compound with epoxy group and unsaturated double bond and the copolymer with the compound of unsaturated double bond react with unsaturated carboxylic acid, then make the generated secondary hydroxyl react with polybasic acid anhydride, thus obtain Carboxyl-containing photosensitive resin; (3) 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 to obtain a carboxyl-containing photosensitive resin; (4) reacting a multifunctional epoxy compound with an unsaturated monocarboxylic acid, and then reacting the generated secondary hydroxyl group with a polybasic anhydride to obtain a carboxyl-containing photosensitive resin; (5) Reaction of a hydroxyl-containing polymer with a polybasic acid anhydride to obtain a carboxyl-containing resin, which is then reacted with a compound having an epoxy group and an unsaturated double bond to obtain a carboxyl-containing photosensitive resin; (6) react the polyfunctional oxetane compound with an unsaturated monocarboxylic acid, and then react the primary hydroxyl group in the obtained modified oxetane resin with a polybasic anhydride to obtain a carboxyl-containing photosensitive Sexual resin. 4. The photocurable and thermosetting resin composition according to claim 1, wherein the maleimide derivative (B) is represented by the following general formula (1) or general formula (2) Aliphatic bismaleimide compounds,

In the formula, m is an integer of 1 to 6, n is a value of 2 to 23, ^R represents a hydrogen atom or a methyl group,

In formula, m represents the integer of 1-6, and p represents the value of 2-14. 5. The photocurable and thermosetting resin composition according to claim 1, wherein the cyclic ether group in the acryloyl or methacryloyl compound (D) is tetrahydrofuran ring, furan ring, tetrahydropyridine Franyl ring, 1,3-dioxolane, 1,3-dioxane or 1,4-dioxane. A cured product obtained by curing the photocurable/thermosetting resin composition according to any one of claims 1 to 5 by irradiating active energy rays and/or heating. 7. A printed wiring board in which an interlayer insulating layer and/or a solder resist layer are formed from the photocurable/thermosetting resin composition according to any one of claims 1 to 5. 8. A printed wiring board in which an optical waveguide layer is formed from the photocurable/thermosetting resin composition according to any one of claims 1 to 5.

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