JP6329738B2 - Curable resin composition, dry film and printed wiring board - Google Patents

Description

  The present invention relates to a curable resin composition, a dry film, and a printed wiring board, and more specifically, a curable resin composition excellent in storage stability despite its one-component property, its dry film, and its cured product. The present invention relates to a printed wiring board provided.

  Due to rapid progress of semiconductor components in recent years, electronic devices tend to be smaller, lighter, higher performance, and multifunctional. Following this trend, printed wiring boards are also becoming increasingly dense and surface-mounted. In the production of high-density printed wiring boards, photo solder resist compositions are generally employed, and dry film type photo solder resist compositions and liquid photo solder resist compositions have been developed. Among these, in consideration of environmental problems, an alkali development type photosensitive resin composition using a dilute alkaline aqueous solution as a developing solution has become mainstream, and several composition systems have been proposed in the past (Patent Documents). 1).

  The alkali-developable photosensitive resin composition exhibits alkali developability by including a carboxyl group-containing resin or the like in the composition. However, the carboxyl group is highly hydrophilic, and when the carboxyl group-containing resin is used in the solder resist composition, the insulation reliability is likely to deteriorate. Therefore, by combining a thermosetting component capable of crosslinking with a carboxyl group represented by an epoxy compound and performing a thermosetting treatment, improvement of characteristics such as insulation reliability and solder heat resistance is achieved.

  Since the carboxyl group and the epoxy group undergo a crosslinking reaction even at room temperature, the carboxyl group-containing resin and the epoxy compound are generally divided into “two-component”. However, the pot life after mixing the two liquids was as short as several hours to one day, and had to be mixed immediately before the coating process. In order to compensate for these two-component defects, various one-component curable resin compositions with improved storage stability have been studied. For example, a photosensitive resin composition comprising a blocked isocyanate compound and a carboxyl group-containing resin, a photopolymerization initiator, a diluent, and an adhesion-imparting agent instead of an epoxy compound has been proposed (see Patent Document 2). In addition, an epoxy resin-encapsulated microcapsule that encapsulates an epoxy compound in a thermally destructible film and latentizes the reaction between the carboxylic acid compound and the epoxy compound at room temperature has been proposed (see Patent Document 3).

JP 61-243869 (Claims etc.) JP 2001-305726 A (Claims etc.) JP 2010-128317 (Claims etc.)

  Various attempts such as addition of various additives and special treatment have been made for the purpose of imparting desired properties suitable for the application to the one-component curable resin composition. Since the storage stability is often impaired by an additive added to improve a certain characteristic or a treatment applied, a one-component curable resin composition having a composition different from the conventional one is obtained. It was sought after.

  Accordingly, an object of the present invention is to provide a curable resin composition having excellent storage stability, a dry film thereof, and a printed wiring board including the cured product, despite being one-component.

  As a result of intensive studies to solve the above problems, the present inventors can store at room temperature by blending a photopolymerization initiator that generates an acid and a radical upon irradiation with light and a thermosetting component. It has been found that a one-component curable resin composition can be obtained.

  That is, the curable resin composition of the present invention contains (A) a photopolymerization initiator that generates an acid and a radical upon irradiation with light, (B) a thermosetting component, and (C) an alkali-soluble resin. It is characterized by this.

  The curable resin composition of the present invention preferably further contains (D) a compound having a plurality of ethylenically unsaturated groups in the molecule.

  In the curable resin composition of the present invention, the (C) alkali-soluble resin preferably has a photosensitive group.

  The curable resin composition of the present invention preferably further contains (E) a colorant.

  In the curable resin composition of the present invention, the (B) thermosetting component is preferably an amino resin.

  The curable resin composition of the present invention is preferably a solder resist forming composition.

  The dry film of the present invention is obtained by coating and drying the curable resin composition on a film.

  The cured product of the present invention is obtained by curing the curable resin composition or the dry film by irradiation with active energy rays.

  The printed wiring board of the present invention comprises the cured product.

  According to the present invention, it is possible to provide a curable resin composition that is excellent in storage stability, a dry film thereof, and a printed wiring board including the cured product regardless of the one-component property.

  The curable resin composition of the present invention contains (A) a photopolymerization initiator that generates an acid and a radical upon irradiation with light, (B) a thermosetting component, and (C) an alkali-soluble resin. It is a feature. By setting it as the said structure, before light irradiation, the thermosetting reaction resulting from (B) thermosetting component does not occur easily, and it is excellent in the storage stability at room temperature. Moreover, even if it does not mix | blend a thermosetting catalyst, favorable thermosetting is exhibited by heating in presence of the acid produced | generated by light irradiation. In addition, when the conventional curable resin composition contains a solvent, in the drying step before light irradiation, the thermosetting component may cause a thermal rash and cannot be developed. If it is an adhesive resin composition, thermal rash is remarkably reduced. Furthermore, since the curable resin composition of this invention is excellent in the storage stability at room temperature, it can be used suitably for formation of a dry film. The cured product obtained by thermosetting has good heat resistance. Hereinafter, each component of the curable resin composition of the present invention will be described in detail.

[(A) Photopolymerization initiator that generates acid and radical by light irradiation]
(A) Any known photopolymerization initiator (hereinafter also simply referred to as “(A) photopolymerization initiator”) that generates an acid and a radical upon irradiation with light can be used. (A) By mix | blending a photoinitiator, not only photosensitivity is provided, but when it heats after the production | generation of the acid by light irradiation, favorable thermosetting will be able to be exhibited now.

  Examples of (A) photopolymerization initiators include 2-phenyl-2- (p-toluenesulfonyloxy) acetophenone, 1-propanone, 1- [4-[(benzoylphenyl) thio] phenyl] -2-methyl- Examples include photopolymerization initiators that generate acids and radicals by irradiation with active energy rays such as 2-[(4-methylphenyl) sulfonyl]. As an example of a commercial item, Tokyo Chemical Industry P1410, Lamberti Esacure 1001M, etc. are mentioned. (A) A photoinitiator can be used individually by 1 type or in combination of 2 or more types.

  (A) As a compounding quantity of a photoinitiator, it is preferable to set it as 0.02-10 wt% of curable resin composition whole quantity in conversion of solid content, and it is more preferable to set it as 0.05-5 wt%. . When it is 0.02 wt% or more, photocurability is good, there is no peeling of the coating film, and coating film properties such as chemical resistance are improved. On the other hand, if it is 10 wt% or less, light absorption on the surface of the coating film is suppressed, and the deep curability tends to be good.

[(B) Thermosetting component]
(B) As a thermosetting component, all well-known things can be used. For example, known and commonly used thermosetting components such as amino resins such as melamine resins, benzoguanamine resins, melamine derivatives and benzoguanamine derivatives, polyol compounds, blocked isocyanate compounds, cyclocarbonate compounds, bismaleimides, oxazine compounds and oxazoline compounds can be used. In addition, an epoxy compound, an oxetane compound or an episulfide resin which is a thermosetting component having a cyclic ether group and / or a cyclic thioether group (hereinafter abbreviated as “cyclic (thio) ether group”) in the molecule may be used. . Among these, the amino resin is preferable because it not only functions as a thermosetting component but also contributes to storage stability because it hardly causes a curing phenomenon at room temperature due to a thermosetting reaction before light irradiation. The curable resin composition of the present invention more preferably contains an amino resin and a polyol compound.

  Examples of the amino resin include melamine derivatives and benzoguanamine derivatives. Examples thereof include a methylol melamine compound, a methylol benzoguanamine compound, a methylol glycol uril compound, a methylol urea compound, an alkoxymethylated melamine compound, an alkoxymethylated benzoguanamine compound, an alkoxymethylated glycoluril compound, and an alkoxymethylated urea compound. Alkoxymethylated melamine compounds, alkoxymethylated benzoguanamine compounds, alkoxymethylated glycoluril compounds, and alkoxymethylated urea compounds are methylol melamine compounds, methylol benzoguanamine compounds, methylol glycoluril compounds, and methylol groups of methylol urea compounds that are alkoxymethyl groups. Can be obtained by converting to The type of the alkoxymethyl group is not particularly limited and can be, for example, a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, a butoxymethyl group, or the like. Among the amino resins, trifunctional or higher functional amino resins are preferable from the viewpoint of curability. Considering the influence on the human body and the environment, a melamine derivative having a formalin concentration of 0.2% or less is preferable. An amino resin can be used individually by 1 type or in combination of 2 or more types.

  Examples of these commercially available products include Cymel 300 manufactured by Mitsui Cyanamid Co., Ltd., 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141, 272, 202, 1156, 1158, 1123, 1170, 1174, UFR65, 300, Nikarak Mx-750, Mx-032, Mx-270, Mx-280, Sanwa Chemical Co., Ltd. Mx-290, Mx-706, Mx-708, Mx-40, Mx-31, Ms-11, Mw-30, Mw-30HM, Mw-390, Mw-100LM, Mw-750LM etc. can be mentioned.

  1-100 mass parts is preferable with respect to 100 mass parts of (C) alkali-soluble resin, and, as for the compounding quantity of the said (B) thermosetting component, 5-50 mass parts is more preferable. The intensity | strength of a coating film improves that it is 1 mass part or more. When it is 100 parts by mass or less, a development residue hardly occurs.

The polyol compound is preferable because the hardness of the cured product can be improved by crosslinking the functional group of the (B) thermosetting component remaining in the reaction with the (C) alkali-soluble resin. The polyol compound is not particularly limited as long as it is a bifunctional or higher functional polyol compound. Examples of bifunctional polyol compounds include ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, spiroglycol, dioxane Glycol, adamantanediol, 3-methyl-1,5-pentanediol, methyloctanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, 2-methylpropanediol, 1,3-methylpentanediol, 1 , 5, hexamethylene glycol, octylene glycol, 9-nonanediol, 2,4-diethyl-1,5-pentanediol, ethylene oxide modified compound of bisphenol A, bisphenol Propylene oxide modified compound of Lumpur A, ethylene oxide of bisphenol A, propylene oxide copolymer modified compound, copolymeric polyether polyol of ethylene oxide and propylene oxide, carbonate diol, polyester polyols, and the like. Examples of the tri- or more functional polyol compound include glycerin, diglycerin, triglycerin, trimethylolethane, trimethylolpropane, sorbitol, pentaerythritol, ditrimethylolpropane, dipentaerythritol, tripentaerythritol, adamantanetriol, and their ethylene oxides, A propylene oxide modified product is also included.
As the polyol compound having an aromatic ring, ethylene oxide of a trifunctional or higher phenol compound, (meth) acrylic acid adduct of a modified propylene oxide; bisphenol A type, bisphenol F type, phenol novolac type, cresol novolac type epoxy resin, etc. (Meth) acrylic acid adducts of bifunctional or higher functional epoxy resins; phenoxy resins and the like.
Examples of the polyol compound having an oxetane ring include a dicarboxylic acid adduct of a polyfunctional oxetane resin, and examples of the polyol compound having a heterocyclic ring include Sake manufactured by Shikoku Kasei Co., Ltd. A polyol compound can be used individually by 1 type or in combination of 2 or more types.

  Although the compounding quantity of a polyol compound is not specifically limited, 1-200 mass parts is preferable with respect to 100 mass parts of (C) alkali-soluble resin, and 10-100 mass parts is more preferable.

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

  Examples of the polyfunctional epoxy compound include bisphenol A type epoxy resin; brominated epoxy resin; novolac type epoxy resin; bisphenol F type epoxy resin; hydrogenated bisphenol A type epoxy resin; glycidylamine type epoxy resin; Cyclic epoxy resin; trihydroxyphenylmethane type epoxy resin; bixylenol type or biphenol type epoxy resin or mixtures thereof; bisphenol S type epoxy resin; bisphenol A novolac type epoxy resin; tetraphenylolethane type epoxy resin; Epoxy resin; diglycidyl phthalate resin; tetraglycidyl xylenoyl ethane resin; naphthalene group-containing epoxy resin; epoxy resin having dicyclopentadiene skeleton; Methacrylate copolymer type epoxy resin; copolymer epoxy resins of cyclohexylmaleimide and glycidyl methacrylate, epoxy-modified polybutadiene rubber derivative; but CTBN modified epoxy resins, but is not limited thereto. These epoxy resins can be used alone or in combination of two or more. Among these, epoxide-modified compounds by the peracetic acid method such as EHPE3150, PB-3600, and Celoxide 2021 (all manufactured by Daicel Chemical Industries, Ltd.) are preferable because they do not contain halogen ions as impurities. The epoxy resin is preferably an alicyclic epoxy resin from the viewpoint of storage stability.

  Examples of the polyfunctional oxetane compound include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [(3-ethyl-3-oxetanylmethoxy) methyl] ether, 1,4-bis [(3-methyl -3-Oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, (3-methyl-3-oxetanyl) methyl acrylate, (3-ethyl-3-oxetanyl) In addition to polyfunctional oxetanes such as methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate and oligomers or copolymers thereof, oxetane alcohol and novolac resin, Poly (p-hydroxystyrene), cardo-type bisphe Lumpur acids, calixarenes, calix resorcin arenes or etherified products such as the resin having a hydroxyl group such as silsesquioxane and the like. In addition, a copolymer of an unsaturated monomer having an oxetane ring and an alkyl (meth) acrylate is also included.

  Examples of the compound having a plurality of cyclic thioether groups in the molecule include bisphenol A type episulfide resin. Moreover, episulfide resin etc. which substituted the oxygen atom of the epoxy group of the novolak-type epoxy resin by the sulfur atom using the same synthesis method can also be used.

  The amount of the thermosetting component having a plurality of cyclic (thio) ether groups in the molecule is preferably 0.1 to 2.5 equivalents per 1 equivalent of the alkali-soluble group of the alkali-soluble resin. More preferably, a range of 0.2 to 2.0 equivalents is appropriate. When the blending amount of the thermosetting component having a plurality of cyclic (thio) ether groups in the molecule exceeds 2.5 equivalents, the low molecular weight cyclic (thio) ether group remains in the dry coating film, This is not preferable because the strength and the like of the product are reduced and the storage stability is also deteriorated. Examples of the alkali-soluble group include a carboxyl group, a phenolic hydroxyl group, and a thiol group.

  As another thermosetting component, a compound having a plurality of isocyanate groups or blocked isocyanate groups in one molecule can be added. Such a compound having a plurality of isocyanate groups or blocked isocyanate groups in one molecule is a compound having a plurality of isocyanate groups in one molecule, that is, a polyisocyanate compound, or a plurality of blocked isocyanate groups in one molecule. The compound which has, ie, a blocked isocyanate compound, etc. are mentioned.

  Examples of the polyisocyanate compound include 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate, o-xylylene diisocyanate, m-xylylene diisocyanate, and Aromatic polyisocyanates such as 2,4-tolylene dimer; Aliphatic polyisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, 4,4-methylenebis (cyclohexyl isocyanate) and isophorone diisocyanate; Alicyclic polyisocyanates such as heptane triisocyanate; and adducts of the isocyanate compounds listed above, Yuretto body and isocyanurate products thereof.

  As the blocked isocyanate compound, an addition reaction product of an isocyanate compound and an isocyanate blocking agent is used. As an isocyanate compound which can react with an isocyanate blocking agent, the above-mentioned polyisocyanate compound etc. are mentioned, for example. As an isocyanate block agent, for example, phenol block agent; lactam block agent; active methylene block agent; alcohol block agent; oxime block agent; mercaptan block agent; acid amide block agent; imide block agent; Examples include amine-based blocking agents; imidazole-based blocking agents; imine-based blocking agents.

  The compounds having a plurality of isocyanate groups or blocked isocyanate groups in one molecule can be used singly or in combination of two or more. The blending amount when blending a compound having a plurality of isocyanate groups or blocked isocyanate groups in one molecule is 1 wt% to 50 wt%, more preferably 2 to 40 wt% of the total amount of the curable resin composition. Proportion is appropriate. When the blending amount is 1 wt% or more, sufficient toughness of the coating film can be obtained. On the other hand, when it is 50 wt% or less, a decrease in storage stability is suppressed.

[(C) Alkali-soluble resin]
(C) As alkali-soluble resin, well-known alkali-soluble resin, such as a phenol resin and a carboxyl group-containing resin, can be used. (C) It is preferable that alkali-soluble resin has a photosensitive group from a photocurable viewpoint. Examples of the photosensitive group include an ethylenically unsaturated group such as a (meth) acryloyl group, an allyl group, a cinnamoyl group, and a cinnamylidene group, an azide group, and the like. Among these, an alkali-soluble resin having an ethylenically unsaturated group is preferable, and a carboxyl group-containing (meth) acrylate is more preferable. When an alkali-soluble resin having no ethylenically unsaturated bond is used, in order to make the composition photocurable, (D) a compound having a plurality of ethylenically unsaturated groups (photosensitive compound) in the molecule is used. Must be used together. In this specification, (meth) acrylic acid is a generic term for acrylic acid, methacrylic acid and mixtures thereof, and the same applies to other similar expressions.

  The alkali-soluble resin is preferably a compound (any of oligomer and polymer) listed below, but is not limited thereto.

  (1) A carboxyl group-containing resin obtained by copolymerization of an unsaturated carboxylic acid such as (meth) acrylic acid and an unsaturated group-containing compound such as styrene, α-methylstyrene, lower alkyl (meth) acrylate, and isobutylene. An alkali-soluble resin obtained by reacting a compound having one or more ethylenically unsaturated groups and one epoxy group in a molecule.

  (2) Diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, and aromatic diisocyanates; carboxyl group-containing dialcohol compounds such as dimethylolpropionic acid and dimethylolbutanoic acid, polycarbonate polyols, and polyethers An alkali-soluble resin obtained by polyaddition reaction of a diol compound such as a polyol, a polyester-based polyol, a polyolefin-based polyol, an acrylic polyol, a bisphenol A-based alkylene oxide adduct diol, a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group.

  (3) Diisocyanate and bifunctional epoxy resin such as bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bixylenol type epoxy resin, biphenol type epoxy resin ( Alkali-soluble resin by polyaddition reaction of (meth) acrylate or its modified partial anhydride, carboxyl group-containing dialcohol compound and diol compound.

  (4) During the synthesis of the resin of the above (2) or (3), a compound having one hydroxyl group and one or more (meth) acryl groups in a molecule such as hydroxyalkyl (meth) acrylate is added, and the terminal ( (Meth) acrylic alkali-soluble resin.

  (5) During the synthesis of the resin of (2) or (3) above, one isocyanate group and one or more (meth) acrylic groups in the molecule, such as an equimolar reaction product of isophorone diisocyanate and pentaerythritol triacrylate An alkali-soluble resin obtained by adding a compound having a terminal (meth) acrylate.

  (6) An alkali-soluble resin obtained by reacting a bifunctional or higher polyfunctional (solid) epoxy resin as described later with (meth) acrylic acid and adding a dibasic acid anhydride to a hydroxyl group present in the side chain.

  (7) A polyfunctional epoxy resin obtained by epoxidizing a hydroxyl group of a bifunctional (solid) epoxy resin as described later with epichlorohydrin is reacted with (meth) acrylic acid, and a dibasic acid anhydride is added to the resulting hydroxyl group. Added alkali-soluble resin.

  (8) A cyclic ether such as ethylene oxide or a cyclic carbonate such as propylene carbonate is added to a polyfunctional phenol compound such as novolak, and the resulting hydroxyl group is partially esterified with (meth) acrylic acid, and the remaining hydroxyl group is An alkali-soluble resin obtained by reacting a basic acid anhydride.

  (9) An alkali-soluble resin obtained by adding a compound having one epoxy group and one or more (meth) acrylic groups in one molecule to the resins (1) to (8).

  Among these, the resins mentioned in (1), (2), modified products thereof (4) and (5), and (8) can be used without using an epoxy compound (resin) made of epichlorohydrin as a raw material. Since a carboxylic acid-containing resin can be synthesized, it is particularly preferable from the viewpoint of halogen-free. In addition, even if it is an epoxy compound (resin), halogen-free can also be achieved by using the epoxy compound (resin) which does not use epichlorohydrin. Furthermore, as long as the isocyanate compound used in the resin synthesis is possible, one using an isocyanate which is not a phosgene method as a raw material is preferable.

  Since the alkali-soluble resin as described above has a large number of carboxyl groups in the side chain of the backbone polymer, development with a dilute aqueous alkali solution is possible.

  The acid value of the alkali-soluble resin is preferably in the range of 40 to 200 mgKOH / g, more preferably in the range of 45 to 120 mgKOH / g. When the acid value of the alkali-soluble resin is 40 mgKOH / g or more, the alkali development is good. On the other hand, when the acid value is 200 mgKOH / g or less, the line is thinned more than necessary, or in some cases, there is no distinction between the exposed part and the unexposed part. This prevents the resist pattern from being dissolved and peeled off by the developer, which makes it difficult to draw a normal resist pattern.

  Moreover, although the weight average molecular weight of the said alkali-soluble resin changes with resin frame | skeleton, what is generally in the range of 2,000-150,000, Furthermore, 5,000-100,000 is preferable. When the weight average molecular weight is 2,000 or more, tack-free performance is improved, moisture resistance of the coated film after exposure is improved, film loss during development is suppressed, and resolution can be improved. On the other hand, when the weight average molecular weight is 150,000 or less, the developability is excellent.

  (C) Alkali-soluble resin can be used individually by 1 type or in combination of 2 or more types. (C) It is preferable that the compounding quantity of alkali-soluble resin is 50 wt% or less of the whole quantity of curable resin composition, and it is more preferable that it is 10-40 wt%.

[(D) Compound having a plurality of ethylenically unsaturated groups in the molecule]
The curable resin composition of the present invention preferably contains (D) a compound having a plurality of ethylenically unsaturated groups in the molecule. (D) The compound having a plurality of ethylenically unsaturated groups in the molecule used in the curable resin composition of the present invention is photocured by irradiation with active energy rays, and the curable resin of the present invention or the above alkali-soluble resin. Is insolubilized in an aqueous alkali solution or assists insolubilization. Examples of such compounds include commonly known polyester (meth) acrylates, polyether (meth) acrylates, urethane (meth) acrylates, carbonate (meth) acrylates, epoxy (meta) having a plurality of ethylenically unsaturated groups in the molecule. ) Acrylates can be used, specifically hydroxyalkyl acrylates; diacrylates of glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, propylene glycol; acrylamides; aminoalkyl acrylates; hexanediol, trimethylol Polyhydric alcohols such as propane, pentaerythritol, dipentaerythritol, tris-hydroxyethyl isocyanurate, etc., or their ethylene oxide adducts, propylene Polyhydric acrylates such as oxide adducts or ε-caprolactone adducts; Phenoxy acrylate, bisphenol A diacrylate, and polyhydric acrylates such as ethylene oxide adducts or propylene oxide adducts of these phenols; Glycerin diglycidyl Polyvalent acrylates of glycidyl ethers such as ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, triglycidyl isocyanurate; not limited to the above, polyols such as polyether polyol, polycarbonate diol, hydroxyl-terminated polybutadiene, polyester polyol Acrylates and melamine acrylates directly acrylated or urethane acrylated via diisocyanate Relates and / or methacrylates corresponding to the above acrylates may be mentioned. (D) The compound which has several ethylenically unsaturated groups in a molecule | numerator can be used individually by 1 type or in combination of 2 or more types.

(D) It is preferable that the compounding quantity of the compound which has a some ethylenically unsaturated group in a molecule | numerator is 1-70 mass% in solid content of a composition, and it is more preferable that it is 5-60 mass%.
Moreover, (D) 5-100 mass parts is preferable with respect to 100 mass parts of (C) alkali-soluble resin, and, as for the compounding quantity of the compound which has a several ethylenically unsaturated group in a molecule | numerator, 5-70 mass parts is. More preferred. When the amount is 5 parts by mass or more, photocurability is improved, and pattern formation is facilitated by alkali development after irradiation with active energy rays. On the other hand, when it is 100 parts by mass or less, the solubility in an alkaline aqueous solution is good, and the strength of the coating film is excellent.

[(E) Colorant]
The curable resin composition of this invention can mix | blend (E) coloring agent. (E) As the colorant, commonly known colorants such as red, blue, green, yellow, white, black and the like can be used, and any of pigments, dyes, and pigments may be used. Specifically, the color index (CI; issued by The Society of Dyers and Colorists) number is given. However, it is preferable not to contain a halogen from the viewpoint of reducing the environmental burden and affecting the human body.

  Examples of the red colorant include monoazo, diazo, azo lake, benzimidazolone, perylene, diketopyrrolopyrrole, condensed azo, anthraquinone, and quinacridone. Examples of blue colorants include metal-substituted or unsubstituted phthalocyanine-based and anthraquinone-based compounds, and pigment-based compounds that are classified as pigments. Green colorants include metal-substituted or unsubstituted phthalocyanine-based, anthraquinone-based, and perylene-based materials. Examples of yellow colorants include monoazo, disazo, condensed azo, benzimidazolone, isoindolinone, and anthraquinone. Examples of the white colorant include rutile type, anatase type titanium oxide and the like. Black colorants include titanium black, carbon black, graphite, iron oxide, anthraquinone, cobalt oxide, copper oxide, manganese, antimony oxide, nickel oxide, perylene, and aniline. Examples thereof include pigments, molybdenum sulfide, and bismuth sulfide. In addition, a colorant such as purple, orange or brown may be added for the purpose of adjusting the color tone.

  (E) Although the compounding quantity of a coloring agent is not specifically limited, It is preferable that it is 5 wt% or less in solid content of a composition, and it is preferable that it is 0.1-3 wt%.

[Other photopolymerization initiators]
Examples of the photopolymerization initiator include an oxime ester photopolymerization initiator having an oxime ester group, an alkylphenone photopolymerization initiator, an α-aminoacetophenone photopolymerization initiator, an acylphosphine oxide photopolymerization initiator, and a titanocene system. One or more photopolymerization initiators selected from the group consisting of photopolymerization initiators can be suitably used. The oxime ester-based initiator is preferable because the addition amount is small and outgassing is suppressed, which is effective in PCT resistance and crack resistance.

（式中、Ｘは、水素原子、炭素数１〜１７のアルキル基、炭素数１〜８のアルコキシ基、フェニル基、フェニル基（炭素数１〜１７のアルキル基、炭素数１〜８のアルコキシ基、
アミノ基、炭素数１〜８のアルキル基を持つアルキルアミノ基またはジアルキルアミノ基により置換されている）、ナフチル基（炭素数１〜１７のアルキル基、炭素数１〜８のアルコキシ基、アミノ基、炭素数１〜８のアルキル基を持つアルキルアミノ基またはジアルキルアミノ基により置換されている）を表し、Ｙ、Ｚはそれぞれ、水素原子、炭素数１〜１７のアルキル基、炭素数１〜８のアルコキシ基、ハロゲン基、フェニル基、フェニル基（炭素数１〜１７のアルキル基、炭素数１〜８のアルコキシ基、アミノ基、炭素数１〜８のアルキル基を持つアルキルアミノ基またはジアルキルアミノ基により置換されている）、ナフチル基（炭素数１〜１７のアルキル基、炭素数１〜８のアルコキシ基、アミノ基、炭素数１〜８のアルキル基を持つアルキルアミノ基またはジアルキルアミノ基により置換されている）、アンスリル基、ピリジル基、ベンゾフリル基、ベンゾチエニル基を表し、Ａｒは、結合か、炭素数１〜１０のアルキレン、ビニレン、フェニレン、ビフェニレン、ピリジレン、ナフチレン、チオフェン、アントリレン、チエニレン、フリレン、２，５−ピロール−ジイル、４，４’−スチルベン−ジイル、４，２’−スチレン−ジイルを表し、ｎは０か１の整数である。） Examples of the oxime ester photopolymerization initiator include CGI-325, Irgacure OXE01, Irgacure OXE02 manufactured by BASF Japan, N-1919, NCI-831 manufactured by ADEKA, and the like as commercially available products. Moreover, the photoinitiator which has two oxime ester groups in a molecule | numerator can also be used suitably, Specifically, the oxime ester compound which has a carbazole structure represented with the following general formula is mentioned.

(In the formula, X is a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenyl group, a phenyl group (an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms). Group,
An amino group, an alkylamino group having an alkyl group having 1 to 8 carbon atoms or a dialkylamino group), a naphthyl group (an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an amino group) Represents an alkylamino group or a dialkylamino group having an alkyl group having 1 to 8 carbon atoms, and Y and Z are each a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, and 1 to 8 carbon atoms. Alkoxy group, halogen group, phenyl group, phenyl group (alkyl group having 1 to 17 carbon atoms, alkoxy group having 1 to 8 carbon atoms, amino group, alkylamino group having 1 to 8 carbon atoms or dialkylamino) A naphthyl group (an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an amino group, an alkyl group having 1 to 8 carbon atoms) An anthryl group, a pyridyl group, a benzofuryl group, a benzothienyl group, Ar is a bond, alkylene having 1 to 10 carbon atoms, vinylene, phenylene, biphenylene, It represents pyridylene, naphthylene, thiophene, anthrylene, thienylene, furylene, 2,5-pyrrole-diyl, 4,4′-stilbene-diyl, 4,2′-styrene-diyl, and n is an integer of 0 or 1. )

  In particular, in the above general formula, X and Y are each a methyl group or an ethyl group, Z is a methyl group or a phenyl group, n is 0, Ar is a bond, phenylene, naphthylene, thiophene or thienylene. It is preferable that

（式中、Ｒ^１は、炭素原子数１〜４のアルキル基、または、ニトロ基、ハロゲン原子もしくは炭素原子数１〜４のアルキル基で置換されていてもよいフェニル基を表す。
Ｒ^２は、炭素原子数１〜４のアルキル基、炭素原子数１〜４のアルコキシ基、または、炭素原子数１〜４のアルキル基もしくはアルコキシ基で置換されていてもよいフェニル基を表す。
Ｒ^３は、酸素原子または硫黄原子で連結されていてもよく、フェニル基で置換されていてもよい炭素原子数１〜２０のアルキル基、炭素原子数１〜４のアルコキシ基で置換されていてもよいベンジル基を表す。
Ｒ^４は、ニトロ基、または、Ｘ−Ｃ（＝Ｏ）−で表されるアシル基を表す。Ｘは、炭素原子数１〜４のアルキル基で置換されていてもよいアリール基、チエニル基、モルホリノ基、チオフェニル基、または、下記式で示される構造を表す。）

Moreover, the compound which can be represented by the following general formula can also be mentioned as a preferable carbazole oxime ester compound.

(In the formula, R ¹ represents an alkyl group or a nitro group, a halogen atom or a phenyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms having 1 to 4 carbon atoms.
R ² represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a phenyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms or an alkoxy group.
R ³ may be linked with an oxygen atom or a sulfur atom, and may be substituted with an alkyl group having 1 to 20 carbon atoms and an alkoxy group having 1 to 4 carbon atoms which may be substituted with a phenyl group. Represents a good benzyl group.
R ⁴ represents a nitro group or an acyl group represented by X—C (═O) —. X represents an aryl group, a thienyl group, a morpholino group, a thiophenyl group, or a structure represented by the following formula, which may be substituted with an alkyl group having 1 to 4 carbon atoms. )

  In addition, JP-A-2004-359639, JP-A-2005-097141, JP-A-2005-220097, JP-A-2006-160634, JP-A-2008-094770, JP-A-2008-509967, Specific examples include carbazole oxime ester compounds described in JP2009-040762A and JP2011-80036A.

The blending amount of such an oxime ester-based photopolymerization initiator is preferably 0.01 to 5 parts by mass and preferably 0.25 to 3 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin. More preferred.
By setting the content to 0.01 to 5 parts by mass, a cured film having excellent photocurability and resolution, improved adhesion and PCT resistance, and excellent chemical resistance such as electroless gold plating resistance is obtained. be able to. In particular, when the amount is 5 parts by mass or less, light absorption on the coating film surface becomes intense, and it is possible to suppress a decrease in deep part curability.

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

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

  Specific examples of the acylphosphine oxide photopolymerization initiator include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and bis (2,6-dimethoxy). And benzoyl) -2,4,4-trimethyl-pentylphosphine oxide. Examples of commercially available products include Lucilin TPO manufactured by BASF, Irgacure 819 manufactured by BASF Japan, and the like.

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

  In addition, Irgacure 389 manufactured by BASF Japan can be suitably used as a photopolymerization initiator. The suitable compounding quantity of Irgacure 389 is 0.1-20 mass parts with respect to 100 mass parts of said carboxyl group-containing resin, More preferably, it is 1-15 mass parts.

A titanocene photopolymerization initiator such as Irgacure 784 can also be suitably used. The suitable compounding quantity of a titanocene type photoinitiator is 0.01-5 mass parts with respect to 100 mass parts of carboxyl group-containing resin, and a more suitable compounding quantity is 0.01-3 mass parts. .
By setting these photopolymerization initiators in suitable amounts, they are excellent in photocurability and resolution, improved in adhesion and PCT resistance, and also in chemical resistance such as electroless gold plating resistance. Solder resist can be used. Moreover, in the case of a suitable blending amount, an effect of reducing outgas is obtained, and further, light absorption on the surface of the coating film becomes intense, so that it is possible to suppress a decrease in deep curability.

  The photosensitive resin composition can use a photoinitiator and a sensitizer in addition to the photopolymerization initiator. Photoinitiators, photoinitiators, and sensitizers that can be suitably used for photosensitive resin compositions include benzoin compounds, acetophenone compounds, anthraquinone compounds, thioxanthone compounds, ketal compounds, benzophenone compounds, and tertiary amine compounds. And xanthone compounds.

  Specific examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether.

  Specific examples of the acetophenone compound include acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, and the like.

  Specific examples of the anthraquinone compound include 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone and the like.

  Specific examples of the thioxanthone compound include 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone, and the like.

  Specific examples of the ketal compound include acetophenone dimethyl ketal and benzyl dimethyl ketal.

  Specific examples of the benzophenone compound include benzophenone, 4-benzoyldiphenyl sulfide, 4-benzoyl-4′-methyldiphenyl sulfide, 4-benzoyl-4′-ethyldiphenyl sulfide, and 4-benzoyl-4′-propyldiphenyl. And sulfides.

  Specifically, as the tertiary amine compound, for example, an ethanolamine compound, a compound having a dialkylaminobenzene structure, such as 4,4′-dimethylaminobenzophenone (Nisso Cure MABP manufactured by Nippon Soda Co., Ltd.), 4, Dialkylaminobenzophenone such as 4′-diethylaminobenzophenone (EAB manufactured by Hodogaya Chemical Co.), 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one (7- (diethylamino) -4-methylcoumarin), etc. Dialkylamino group-containing coumarin compound, ethyl 4-dimethylaminobenzoate (Kayacure EPA manufactured by Nippon Kayaku Co., Ltd.), ethyl 2-dimethylaminobenzoate (Quantacure DMB manufactured by International Bio-Synthetics), 4-dimethylamino Ethyl benzoate (n-butoxy) ethyl (Quantacure BEA, manufactured by International Bio-Synthetics), p-dimethylaminobenzoic acid isoamyl ethyl ester (Kayacure DMBI, manufactured by Nippon Kayaku Co., Ltd.), 2-ethylhexyl 4-dimethylaminobenzoate (Esolol 507 manufactured by Van Dyk), 4,4′-diethylaminobenzophenone (EAB manufactured by Hodogaya Chemical Co., Ltd.) and the like.

  Of these, thioxanthone compounds and tertiary amine compounds are preferred. In particular, the inclusion of a thioxanthone compound is preferable from the viewpoint of deep curability. Among them, it is preferable to contain a thioxanthone compound such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone.

  As a compounding quantity of such a thioxanthone compound, it is preferable that it is 20 mass parts or less with respect to 100 mass parts of said carboxyl group-containing resin. When the blending amount of the thioxanthone compound is 20 parts by mass or less, the thick film curability is improved and the cost of the product is reduced. More preferably, it is 10 parts by mass or less.

  As the tertiary amine compound, a compound having a dialkylaminobenzene structure is preferable, and among them, a dialkylaminobenzophenone compound, a dialkylamino group-containing coumarin compound having a maximum absorption wavelength in the range of 350 to 450 nm, and ketocoumarins are particularly preferable. .

  As the dialkylaminobenzophenone compound, 4,4'-diethylaminobenzophenone is preferable because of its low toxicity. Dialkylamino group-containing coumarin compounds have a maximum absorption wavelength in the ultraviolet region of 350 to 410 nm, so they are less colored, and use colored pigments as well as colorless and transparent photosensitive compositions, and colors that reflect the color of the colored pigments themselves It becomes possible to provide a solder resist. In particular, 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one is preferable because it exhibits an excellent sensitizing effect on laser light having a wavelength of 400 to 410 nm.

  As a compounding quantity of such a tertiary amine compound, it is preferable that it is 0.1-20 mass parts with respect to 100 mass parts of said carboxyl group-containing resin. When the compounding amount of the tertiary amine compound is 0.1 parts by mass or more, a sufficient sensitizing effect can be obtained. On the other hand, when the amount is 20 parts by mass or less, light absorption on the surface of the dried coating film by the tertiary amine compound becomes violent, and it is suppressed that the deep part curability is lowered. More preferably, it is 0.1-10 mass parts.

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

(Adhesion promoter)
In the curable resin composition of the present invention, an adhesion promoter can be blended in order to improve adhesion between layers or adhesion with a substrate. Examples of the adhesion promoter include benzimidazole, benzoxazole, benzthiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzthiazole, 3-morpholinomethyl-1-phenyl-triazole-2-thione, 5- Amino-3-morpholinomethyl-thiazole-2-thione, 2-mercapto-5-methylthio-thiadiazole, triazole, tetrazole, benzotriazole, carboxybenzotriazole, amino group-containing benzotriazole, vinyltriazine, silane coupling agent, etc. It is done.

  An adhesion promoter can be used individually by 1 type or in combination of 2 or more types. Although the compounding quantity of an adhesion promoter is not specifically limited, 0.05-10 mass parts is preferable with respect to 100 mass parts of (C) alkali-soluble resin, and 0.1-5 mass parts is more preferable. In the case of 0.05 part by mass or more, a sufficient adhesion promoting effect is obtained. In the case of 10 parts by mass or less, a decrease in storage stability can be suppressed.

(Filler)
The curable resin composition of the present invention can contain a filler as necessary in order to increase the physical strength of the coating film. As such a filler, known and commonly used inorganic or organic fillers can be used, and in particular, barium sulfate, spherical silica, Neuburg silica and talc are preferably used. Furthermore, in order to obtain a white appearance and flame retardancy, metal hydroxides such as titanium oxide, metal oxide, and aluminum hydroxide can be used as extender pigment fillers. A filler can be used individually by 1 type or in combination of 2 or more types. The blending amount of the filler is preferably 75 wt% or less, more preferably 0.1 to 60 wt% of the total amount of the curable resin composition. When the blending amount of the filler is 75 wt% or less of the total amount of the composition, it is possible to reduce the viscosity of the insulating composition to improve application and moldability, and to prevent the cured product from becoming brittle.

(Thermosetting catalyst)
In the curable resin composition of the present invention, a thermosetting catalyst can be blended as necessary. However, since (A) a good curability is obtained by blending the photopolymerization initiator, from the viewpoint of cost. It is preferable that a small amount is not blended or even if blended. The blending amount of the thermosetting catalyst is preferably 0 to 5 parts by mass and more preferably 0 to 3 parts by mass with respect to 100 parts by mass of the (C) alkali-soluble resin. The thermosetting catalyst is not particularly limited as long as it accelerates the curing of the amino resin, but paratoluenesulfonic acid or the like can be suitably used.

(Organic solvent)
In the curable resin composition of the present invention, the viscosity adjustment for (B) thermosetting component or (C) synthesis of alkali-soluble resin, preparation of the composition, or application to a substrate or a carrier film. Therefore, an organic solvent can be used. Examples of such an organic solvent include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, petroleum solvents, and the like. More specifically, ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl Glycol ethers such as ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether; ethyl acetate, butyl acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate , Propylene glycol ethyl ether acetate, propylene glycol butyl ether Esters such as cetate and methyl 2-hydroxyisobutyrate; alcohols such as ethanol, propanol, ethylene glycol, and propylene glycol; aliphatic hydrocarbons such as octane and decane; petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha Petroleum-based solvents such as An organic solvent can be used individually by 1 type or in combination of 2 or more types.

(Other optional ingredients)
In the curable resin composition of the present invention, if necessary, a cyanate compound, an elastomer, a mercapto compound, a urethanization catalyst, a thixotropic agent, an adhesion promoter, a block copolymer, a chain transfer agent, a polymerization inhibitor, Copper damage inhibitor, antioxidant, rust inhibitor, ultraviolet absorber, fine silica, organic bentonite, montmorillonite and other thickeners, silicone-based, fluorine-based, polymer-based antifoaming agents and / or leveling agents, Components such as flame retardants such as imidazole, thiazole and triazole silane coupling agents, phosphinic acid salts, phosphoric ester derivatives and phosphorous compounds such as phosphazene compounds can be blended. As these, those known in the field of electronic materials can be used.

  The curable resin composition of the present invention is suitable for forming a cured film such as a solder resist or an interlayer insulating layer of a printed wiring board or a flexible printed wiring board. Moreover, since it is excellent in storage stability, it can be preferably used as a curable resin composition for dry films.

  The curable resin composition of the present invention is adjusted to a viscosity suitable for the coating method with the organic solvent, for example, on the substrate, dip coating method, flow coating method, roll coating method, bar coater method, screen printing method, A tack-free coating film can be formed by applying the organic solvent contained in the composition at a temperature of about 60 to 100 ° C. by volatile drying (preliminary drying) at a temperature of about 60 to 100 ° C. Moreover, a resin insulation layer can be formed by apply | coating the said composition on a carrier film, and drying and winding up as a film together on a base material. Thereafter, by a contact method (or non-contact method), exposure is selectively performed with an active energy ray through a photomask having a pattern formed thereon or direct pattern exposure is performed by a laser direct exposure machine, and an unexposed portion is diluted with a dilute alkaline aqueous solution (for example, 0.3 The resist pattern is formed by development with a 3 wt% sodium carbonate aqueous solution. Furthermore, for example, by heating to a temperature of about 140 to 180 ° C. and thermosetting, the carboxyl group or phenolic hydroxyl group of the (C) alkali-soluble resin reacts with (B) the thermosetting component, A cured coating film excellent in various properties such as chemical resistance, moisture absorption resistance, adhesion, and electrical properties can be formed.

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

  Volatile drying performed after the application of the curable resin composition of the present invention is performed in a dryer using a hot air circulation drying furnace, an IR furnace, a hot plate, a convection oven or the like (equipped with a heat source of an air heating method using steam). The method can be carried out using a method in which hot air is brought into countercurrent contact and a method in which the hot air is blown onto the support.

  After applying the curable resin composition of the present invention and evaporating and drying as described above, the obtained coating film is exposed (irradiated with active energy rays). In the coating film, the exposed portion (the portion irradiated by the active energy ray) is cured.

As the exposure apparatus used for the active energy ray irradiation, a direct drawing apparatus (for example, a laser direct imaging apparatus that directly draws an image with a laser using CAD data from a computer), an exposure apparatus equipped with a metal halide lamp, and an (ultra) high pressure mercury lamp. , An exposure machine equipped with a mercury short arc lamp, or a direct drawing apparatus using an ultraviolet lamp such as a (super) high pressure mercury lamp. As the active energy ray, either a gas laser or a solid laser may be used as long as laser light having a maximum wavelength in the range of 350 to 410 nm is used. Further, the exposure amount varies depending the thickness or the like, generally 5~800mJ / cm ^2, preferably be in the range of 5~500mJ / cm ^2. As the direct drawing device, for example, those manufactured by Nippon Orbotech, Pentax, etc. can be used, and any device may be used as long as it oscillates laser light having a maximum wavelength of 350 to 410 nm. .

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

  The curable resin composition of the present invention is in the form of a dry film having a solder resist layer formed by applying and drying a solder resist in advance on a film of polyethylene terephthalate or the like, in addition to a method of directly applying to a substrate in a liquid state. It can also be used. The case where the curable resin composition of this invention is used as a dry film is shown below.

  For example, a dry film for forming a solder resist has a structure in which a carrier film, a solder resist layer, and a peelable cover film used as necessary are laminated in this order. The solder resist layer is a layer obtained by applying and drying a curable resin composition on a carrier film or a cover film. After forming a solder resist layer on the carrier film, a cover film is laminated thereon, or a solder resist layer is formed on the cover film, and this laminate is laminated on the carrier film to obtain a dry film.

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

  To produce a protective film (permanent protective film) on a printed wiring board using a dry film, peel off the cover film, layer the solder resist layer and the substrate on which the circuit is formed, and bond them together using a laminator, etc. A solder resist layer is formed on the formed substrate. If the formed solder resist layer is exposed, developed, and heat cured in the same manner as described above, a cured coating film can be formed. The carrier film may be peeled off either before exposure or after exposure.

  A dry film for forming an interlayer insulating layer can be produced by providing an interlayer insulating layer instead of the solder resist layer.

  EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to the following examples. In the following, “part” and “%” are based on mass unless otherwise specified.

(Synthesis Example 1)
Orthocresol novolac type epoxy resin [EPICLON N-695 manufactured by DIC, softening point 95 ° C., epoxy equivalent 214, average functional group number 7.6] 1070 g, 360 g of acrylic acid, and 1.5 g of hydroquinone were added to 600 g of diethylene glycol monoethyl ether acetate. The mixture was heated and stirred at 100 ° C. to dissolve uniformly. Next, 4.3 g of triphenylphosphine was charged, heated to 110 ° C. and reacted for 2 hours, then heated to 120 ° C. and reacted for further 12 hours. 415 g of aromatic hydrocarbon (Sorvesso 150) and 456.0 g of tetrahydrophthalic anhydride were added to the resulting reaction liquid, reacted at 110 ° C. for 4 hours, and after cooling, the solid content acid value 89 mgKOH / g, solid content 65 % Resin solution was obtained. This is designated as resin solution C-1.

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

(Examples 3, 4, Reference Examples 1, 2, 5-8, Comparative Examples 1-3)
It mix | blended with the ratio (mass part) shown in Table 1 with the various components shown in following Table 1, Then, it knead | mixed with the 3 roll mill after premixing with the stirrer, and prepared the resin composition.

＊１：１−プロパノン，１−［４−［（ベンゾイルフェニル）チオ］フェニル］−２−メチル−２−［（４−メチルフェニル）スルホニル］（Ｌａｍｂｅｒｔｉ社製Ｅｓａｃｕｒｅ １００１Ｍ）
＊２：パラトルエンスルホン酸
＊３：（Ａ）光重合開始剤ではない光重合開始剤（アシルフォスフィンオキサイド系光重合開始剤）（シーベルヘグナー社製スピードキュアＴＰＯ）
＊４：メチル化メラミン樹脂（メトキシメチル化メラミン化合物）（三和ケミカル社製ニカラックＭＷ−１００ＬＭ）
＊５：メチル化メラミン樹脂（メトキシメチル化メラミン化合物）（三和ケミカル社製ニカラックＭＷ−３９０）
＊６：メチル化メラミン樹脂（メトキシメチル化メラミン化合物）（三和ケミカル社製ニカラックＭＸ−７５０ＬＭ）
＊７：メチル化尿素樹脂（メトキシメチル化尿素化合物）（三和ケミカル社製ニカラックＭＸ−２７０）
＊８：ポリエステルポリオール（東洋紡社製バイロン５６０、水酸基価 ８ｍｇＫＯＨ／ｇ）
＊９：ポリカーボネートジオール（旭化成ケミカルズ社製ＤＵＲＡＮＯＬ Ｔ５６５０Ｊ、水酸基価 １４５ｍｇＫＯＨ／ｇ）
＊１０：２，２−ビス（ヒドロキシメチル）−１−ブタノールの１，２−エポキシ−４−（２−オキシラニル）シクロヘキサン付加物（ダイセル化学社製ＥＨＰＥ−３１５０）
＊１１：１−ベンジル−２−フェニルイミダゾール（四国化成社製キュアゾール１Ｂ２ＰＺ）
＊１２：ジペンタエリスリトールヘキサアクリレート（日本化薬社製ＫＡＹＡＲＡＤ ＤＰＨＡ）
＊１３：硫酸バリウム（堺化学社製Ｂ−３０）
＊１４：Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｂｌｕｅ １５：３
＊１５：Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｙｅｌｌｏｗ １４７

* 1: 1-propanone, 1- [4-[(benzoylphenyl) thio] phenyl] -2-methyl-2-[(4-methylphenyl) sulfonyl] (Esacure 1001M manufactured by Lamberti)
* 2: Paratoluenesulfonic acid * 3: (A) Photopolymerization initiator that is not a photopolymerization initiator (acylphosphine oxide photopolymerization initiator) (Speed Cure TPO manufactured by Sebel Hegner)
* 4: Methylated melamine resin (methoxymethylated melamine compound) (Nikarak MW-100LM manufactured by Sanwa Chemical Co., Ltd.)
* 5: Methylated melamine resin (methoxymethylated melamine compound) (Nikarak MW-390 manufactured by Sanwa Chemical Co., Ltd.)
* 6: Methylated melamine resin (methoxymethylated melamine compound) (Nikarak MX-750LM manufactured by Sanwa Chemical Co., Ltd.)
* 7: Methylated urea resin (methoxymethylated urea compound) (Nikalac MX-270, manufactured by Sanwa Chemical Co., Ltd.)
* 8: Polyester polyol (Byonbo Co., Ltd. Byron 560, hydroxyl value 8 mgKOH / g)
* 9: Polycarbonate diol (DURANOL T5650J, manufactured by Asahi Kasei Chemicals Corporation, hydroxyl value 145 mgKOH / g)
* 10: 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol (EHPE-3150 manufactured by Daicel Chemical Industries)
* 11: 1-benzyl-2-phenylimidazole (Cureazole 1B2PZ manufactured by Shikoku Chemicals)
* 12: Dipentaerythritol hexaacrylate (KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd.)
* 13: Barium sulfate (B-30, Sakai Chemical Co., Ltd.)
* 14: C.I. I. Pigment Blue 15: 3
* 15: C.I. I. Pigment Yellow 147

About the resin composition of the Example , reference example, and comparative example which are shown in Table 1, performance evaluation and characteristic evaluation were performed with the evaluation method shown below. The evaluation results are shown in Table 2.

<Storage stability>
The resin compositions of Examples , Reference Examples and Comparative Examples in Table 1 were stored in a dark place at 50 ° C., and the viscosity increase rate over time was measured. When the thickening ratio exceeded 200%, it was determined that the product could not be used, and the time until the product was not used was measured. Judgment criteria are as follows.
○: The viscosity increase rate is 200% or less even after 200 hours.
(Triangle | delta): The viscosity increase rate is 200% or less when 100 hours pass, and the viscosity increase rate exceeds 200% when 200 hours pass.
X: The viscosity increase rate exceeds 200% after 100 hours.

<Gelification test>
After the copper solid substrate was polished with buffalo, washed with water and dried , the resin compositions of the above-mentioned Examples , Reference Examples and Comparative Examples were applied to the entire surface by a screen printing method, and 60 minutes in an 80 ° C. hot air circulation drying oven. Dried. After drying, exposure was performed at an exposure amount of 1 J / cm ² using an exposure apparatus equipped with a high-pressure mercury lamp (short arc lamp). The exposed coating film was scraped off, and 1 g of the coating film was subjected to a gelation test machine preheated to 150 ° C., and the time until gelation was measured. Judgment criteria are as follows.
○: Gelation occurs within 30 minutes.
X: Gelation is not confirmed even if it exceeds 30 minutes.

<Optimum exposure amount>
A circuit pattern substrate having a copper thickness of 35 μm was polished with buffalo, washed with water and dried, and then the resin compositions of Examples , Reference Examples and Comparative Examples were applied to the entire surface by screen printing, and dried at 80 ° C. with hot air circulation. Dry in an oven for 60 minutes. After drying, exposure is performed through a step tablet (Kodak No. 2) using an exposure apparatus equipped with a high-pressure mercury lamp (short arc lamp), and development (30 ° C., 0.2 MPa, 1 wt% Na ₂ CO ₃ aqueous solution) is performed at 60. When the pattern of the step tablet remaining when performing in seconds was 7 steps, the optimum exposure amount was set.

Characteristic evaluation substrate manufacturing procedure:
The resin compositions of Examples , Reference Examples, and Comparative Examples shown in Table 1 were applied onto the patterned copper foil substrate by screen printing, dried at 80 ° C. for 30 minutes, and allowed to cool to room temperature. Thereafter, a solder resist pattern is exposed at an optimum exposure amount using an exposure apparatus equipped with a high-pressure mercury lamp (short arc lamp) on this substrate, and a 1 wt% Na ₂ CO ₃ aqueous solution at 30 ° C. is applied under a spray pressure of 2 kg / cm ² . Development was performed for 60 seconds to obtain a resist pattern. This substrate was irradiated with ultraviolet rays under a condition of an integrated exposure amount of 1000 mJ / cm ^{2 in} a UV conveyor furnace, and then cured by heating at 150 ° C. for 60 minutes to form a cured coating film. The characteristics of the obtained printed circuit board (evaluation board) were evaluated as follows.

<PCT resistance>
The said evaluation board | substrate was processed for 100 hours on the conditions of 121 degreeC, saturation, and 0.2 MPa using the PCT apparatus (Espec company make HAST SYSTEM TPC-412MD), and the state of the coating film was evaluated. Judgment criteria are as follows.
○: No swelling or peeling.
X: Some swelling or peeling.

<Surface pencil hardness>
The said evaluation board | substrate was measured on condition of the following according to JIS-K5600 (1999) using the measuring apparatus (Toyo Seiki company_made: pencil scratch coating-film hardness tester).
・ Load: 750g
・ Measurement speed: 30mm / min
・ Measurement distance: 7mm
-Mitsubishi pencil make: UNI was used as a pencil.
The measurement was made 5 times, and the softness of the pencil hardness that was scratched twice or more was defined as the pencil hardness of the measurement substance. Judgment criteria are as follows.
A: 5H or more O: 3H or more and less than 5H Δ: H or more and less than 3H.
X: Less than H.

From the results shown in Tables 1 and 2 above, the curable resin compositions of Examples 3 and 4 and Reference Examples 1, 2 and 5 to 8 are excellent in storage stability in spite of being one-component, and thermosetting. It turned out that it is excellent in sclerosis | hardenability, without mix | blending a catalyst. Moreover, PCT tolerance is also favorable and it turns out that there is little deterioration of the coating film by a heat | fever. On the other hand, instead of (A) the photopolymerization initiator, Comparative Examples 1 and 2 using a thermosetting catalyst and Comparative Example 3 using a thermosetting resin were inferior in storage stability.

  As described above, the curable resin composition of the present invention is excellent in storage stability in spite of being one-component, so that it may be useful for forming a cured coating film such as a solder resist or an interlayer insulating layer. I understand.

Claims (7)

(A) a photopolymerization initiator that generates an acid and a radical by light irradiation;
(B) a thermosetting component, and
(C) an alkali-soluble resin,
A curable resin composition containing
A curable resin composition for forming a one-part solder resist , comprising an amino resin and a polyol compound as the thermosetting component (B).   The curable resin composition for forming a one-component solder resist according to claim 1, further comprising (D) a compound having a plurality of ethylenically unsaturated groups in the molecule.   The curable resin composition for forming a one-component solder resist according to claim 1 or 2, wherein the (C) alkali-soluble resin has a photosensitive group.   The curable resin composition for forming a one-component solder resist according to any one of claims 1 to 3, further comprising (E) a colorant.   A dry film obtained by applying and drying the one-component curable resin composition for forming a solder resist according to any one of claims 1 to 4 on a film.   It is obtained by curing the one-component solder resist-forming curable resin composition according to any one of claims 1 to 4 or the dry film according to claim 5 by active energy ray irradiation. Cured product.   A printed wiring board comprising the cured product according to claim 6.