JP2005120142A - Curable composition, its cured product, and printed wiring board using it - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable composition, especially a photo-curable thermosetting composition, which is excellent in storage stability, of which the curing reaction proceeds rapidly at its curing temperature, and which can form a cured film excellent in characteristics, such as electrical insulation properties, without causing cure shrinkage in a coating film; and a printed wiring board having a solder resist and/or an insulating layer in between conductor circuit layers, formed from the cured product. <P>SOLUTION: The curable composition contains (A) a carboxy-group-containing resin, (B) a compound having an oxetanyl group, and (C) an acetylacetone-metal complex. The photo-curable thermosetting composition further contains (D) a compound having a polymerizable unsaturated double bond and (E) a photopolymerization initiator in addition to the above components. In a suitable embodiment, both of the above compositions further contain (F) an s-triazine compound and/or a dicyandiamide in addition to the above components. The compositions may be in a liquid state or a dry film state. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a curable composition in a liquid form or a dry film form suitable for applications such as circuit board manufacture and mounting on electronic components, and a cured product thereof, and more particularly, a consumer or industrial printed wiring board solder. The present invention relates to a curable composition suitable for forming a resist, an insulating layer between conductor circuit layers, and the like, in particular, a photocurable / thermosetting composition and a cured product thereof. The present invention also relates to a printed wiring board in which an insulating layer between a solder resist and / or a conductor circuit layer is formed by a cured product of such a composition.

  Epoxy resins typified by bisphenol A type epoxy resins have excellent adhesion, heat resistance, chemical resistance, and electrical insulation, and thus have been widely used for adhesives, resists, casting agents, laminates, It is used for applications such as paints and sealants. However, with the development of the electrical industry and the semiconductor industry, for example, improvement in characteristics such as heat resistance, toughness, water resistance, and chemical resistance has been required, and various epoxy resins have been proposed to satisfy such characteristics. For example, polynuclear epoxy resins such as cresol novolac type epoxy resins and phenol novolac type epoxy resins have been proposed as epoxy resins having excellent heat resistance. However, although these epoxy resins are certainly excellent in heat resistance, they have a drawback that they are susceptible to cracking due to thermal shock because they have large shrinkage upon curing, little elongation, and lack toughness.

  In general, in a printed wiring board for consumer use or industrial use, a solder resist is formed for the purpose of preventing solder non-sticking to unnecessary portions and circuit protection when supplying solder when mounting electronic components. As a resin composition for this solder resist, a development type solder resist composition that forms a pattern by a photolithography method is widespread from the viewpoint of high accuracy and high density, and in particular, from the viewpoint of environment and cost. Alkali development type solder resist compositions using dilute aqueous alkali solutions are the mainstream.

  In order to improve solder heat resistance etc., such a solder resist composition usually contains a polyfunctional epoxy resin having two or more epoxy groups as a thermosetting component. However, since this polyfunctional epoxy resin is highly reactive, the photo-curable / thermosetting resin composition containing it has a short shelf life (thus life) and thickens before application to a circuit board blank. Therefore, it is difficult to make a one-component composition. Therefore, it is composed of a two-part composition consisting mainly of a curing agent solution mainly composed of a polyfunctional epoxy resin and a photosensitive prepolymer, which is blended with a curing accelerator, etc., and these are mixed for use. There was a problem in terms of workability.

Moreover, in the photocurable thermosetting resin composition containing a polyfunctional epoxy resin soluble in an organic solvent, the epoxy resin is dissolved in an entangled state with the photosensitive prepolymer. Therefore, when the coating film is exposed and the unexposed part is developed, the solubility of the photosensitive prepolymer is reduced due to the entanglement, and the reaction is accelerated because the epoxy resin is dissolved in the solvent. Further, there is a problem that a phenomenon in which a development residue is generated at the time of development, that is, so-called “hot fog” easily occurs and developability is deteriorated.
Furthermore, when the curable resin composition containing a polyfunctional epoxy resin is in the form of a dry film, there is a problem in storage stability at room temperature and shelf life (storage life) is shortened. There was a need.

In recent years, oxetane compounds have attracted attention as compounds that do not have such problems and can replace epoxy resins. From the viewpoint of creating new organic reactions and applying them to polymer synthesis, organic reactions using ring-opening addition reactions of oxetane rings, which are 4-membered ring ethers, have been studied. For example, oxetane compounds and active esters Studies have been made and reported on the synthesis of polyesters having a primary hydroxyl group in the side chain (see Non-Patent Document 2) by the addition reaction (see Non-Patent Document 1) and polyaddition reaction of bisoxetane and dicarboxylic acid. More recently, a polyaddition reaction between bisoxetanes and bisphenols (see Non-Patent Document 3) has been reported, and Patent Document 1 discloses a thermosetting composition containing an oxetane compound and a polycarboxylic acid. However, in any case, in specific examples, a quaternary onium salt having a halogen ion such as tetraphenylphosphonium bromide (TPPB) as an anion species is used as a catalyst for the curing reaction.
T. Nishikubo and K. Sato, Chem. Lett., 697 (1991) T. Nishikubo, A. Kameyama, A. Suzuki, Reactive & Functional Polymers, 37, 19 (1998) T. Nishikubo, A. Kameyama, M. Ito, T. Nakajima, H. Miyazaki, Journal of Polymer Chemistry, Vol. 37, pp. 2781-2790 (1999) JP-A-11-43540 (Claims)

  However, as in the past, a curable composition of an oxetane compound using a quaternary onium salt having a halogen ion such as tetraphenylphosphonium bromide (TPPB) as an anion species as a catalyst for the curing reaction is in terms of curing reactivity. It has not yet reached a satisfactory level, and the presence of halogen ions has a problem in terms of electrical characteristics, which has hindered practical application to printed wiring boards having conductor circuits.

Therefore, the object of the present invention is that there is no problem due to the use of an epoxy resin as a thermosetting component as described above, and it has the advantages of an oxetane compound used in place of it as it is, and a conventional quaternary onium salt as a catalyst. There is no problem when used, it is excellent in storage stability, the curing reaction proceeds rapidly at the curing temperature, the coating shrinkage does not occur, and a cured film excellent in various properties such as electrical insulation is obtained. It is providing the curable composition which can be formed, and the hardened | cured material with high insulation reliability formed using it.
Another object of the present invention is that there is no problem as described above, it is excellent in storage stability and can be composed in a one-pack type, and the life during development is long (development work margin is large). , A photo-curing and thermosetting composition that can form a cured film with excellent properties such as electrical insulation, heat resistance, and adhesiveness, as well as excellent developability, and without causing hot fog or shrinkage of the coating film. And providing a cured product thereof.
Furthermore, the object of the present invention is to provide high insulation reliability in which an insulating layer between a solder resist and / or a conductor circuit layer is formed from a curable composition as described above, in particular, a cured product of a photocurable / thermosetting composition. It is to provide a printed wiring board.

In order to achieve the above object, according to the first aspect of the present invention, (A) a carboxyl group-containing resin, (B) a compound having an oxetanyl group (hereinafter referred to as “oxetane compound”), and (C). A curable composition characterized by containing an acetylacetone metal complex is provided. Here, the metal complex is a concept including a metal complex salt.
According to the second aspect of the present invention, (A) a carboxyl group-containing resin, (B) an oxetane compound, (C) an acetylacetone metal complex, (D) a compound containing a polymerizable unsaturated double bond, and ( E) A photocurable / thermosetting composition comprising a photopolymerization initiator is provided.
In a preferred embodiment, the composition contains (F) s-triazine compound and / or dicyandiamide in addition to the components described above.
The curable composition or the photocurable / thermosetting composition may be in a liquid form or a dry film.
Furthermore, according to this invention, the hardened | cured material obtained by hardening | curing the said curable composition or a photocurable thermosetting composition, or also an insulating layer between a solder resist and / or a conductor circuit layer is formed with this hardened | cured material. A printed wiring board is provided.

Since the curable composition and the photocurable / thermosetting composition of the present invention use an acetylacetone metal complex as a catalyst of a curing reaction system containing an oxetane compound as a thermosetting component, it has excellent storage stability. In addition, the curing reaction proceeds rapidly at the curing temperature, and the obtained cured product is excellent in electrical characteristics. That is, the curable composition and the photocurable / thermosetting composition of the present invention are inferior in storage stability when using an epoxy resin as a conventional thermosetting component, and the coating film undergoes curing shrinkage. There is no problem of inferior electrical properties when using a conventional quaternary onium salt as a catalyst while having the advantages of the oxetane compound used in place of it as it is, electrical insulation, heat resistance, plating resistance, It can form cured films with excellent properties such as hardness, crack resistance (toughness), and adhesion, and can be used for various applications such as resist materials, sealants, adhesives, paints, printing inks, especially printed wiring board solder. It is useful as a resist and an interlayer insulation material for build-up multilayer printed wiring boards. Furthermore, since a dry film excellent in storage stability at room temperature can be produced, it is advantageous in terms of workability.
In addition, the photocurable / thermosetting composition of the present invention has a long life during development (large work margin for development), excellent developability, and excellent storage stability. Furthermore, since a photosensitive dry film excellent in storage stability at room temperature can be produced, it is advantageous in terms of workability. In addition, various resists can be obtained because cured products excellent in various properties such as crack resistance (toughness), adhesion, hardness, solder heat resistance, and electrical insulation properties can be obtained without causing thermal fogging or curing shrinkage of the coating film. It is useful as a material or an insulating material, particularly a solder resist for a printed wiring board or an interlayer insulating material for a build-up multilayer printed wiring board.

  As a result of intensive studies on a catalyst having high activity and not deteriorating electrical characteristics as a reaction catalyst for oxetanyl group and carboxyl group, the present inventors have found that acetylacetone as a curing catalyst for a curable composition containing a carboxyl group-containing resin and an oxetane compound. It has been found that when a metal complex is used, a cured product having excellent storage stability and electrical characteristics can be obtained, and the present invention has been completed. Another advantage of using an acetylacetone metal complex as the catalyst is that the curability at the curing temperature is good.

Moreover, the curable composition containing an oxetane compound together with a carboxyl group-containing resin has no disadvantages when an epoxy resin is used as a thermosetting component as in the prior art, and can enjoy the advantages of using an oxetane compound.
That is, the oxetane compound added as a thermosetting component to the curable composition and the photocurable / thermosetting composition of the present invention has a four-membered oxetanyl group, which is a carboxyl group-containing resin during thermosetting. Since primary hydroxyl groups are mainly generated by reacting with the carboxyl group of the resin, a cured film with excellent adhesion to the substrate can be obtained compared with the case of using a polyfunctional epoxy compound that mainly generates secondary hydroxyl groups. At the same time, because of the four-membered ring, the amount of ethylene units after the reaction is small, so the volume shrinkage is small, and the toughness is excellent. In addition, since the polyfunctional oxetane compound has a relatively low reactivity at a relatively low temperature as compared with the polyfunctional epoxy compound, the photocurable / thermosetting composition containing the polyfunctional oxetane compound has a long shelf life (storage life). It is possible to create a photosensitive dry film that can be composed in liquid form and can be stored at room temperature, and workability can be improved by using such a one-part photocurable / thermosetting composition or photosensitive dry film. In addition, there is an advantage that the development life is long and the heat fog hardly occurs.
Furthermore, by adding an s-triazine compound and / or dicyandiamide to the curable composition and the photocurable / thermosetting composition of the present invention, gold plating resistance, discoloration resistance, and adhesion to a substrate are further improved. Further improvement.

Hereinafter, each component of the curable composition and the photocurable / thermosetting composition of the present invention will be described in detail.
First, the carboxyl group-containing resin (A) includes a resin having a carboxyl group, specifically, a carboxyl group-containing photosensitive resin having an ethylenically unsaturated double bond and an ethylenically unsaturated double bond. Any of the carboxyl group-containing resins that are not used can be used, and is not limited to a specific one, but in particular, resins (any of oligomers and polymers) listed below can be preferably used.

(1) a carboxyl group-containing resin obtained by copolymerizing an unsaturated carboxylic acid (a) and a compound (b) having an unsaturated double bond,
(2) a carboxyl group-containing photosensitive resin obtained by adding an ethylenically unsaturated group as a pendant to a copolymer of an unsaturated carboxylic acid (a) and a compound (b) having an unsaturated double bond,
(3) A secondary product produced by reacting an unsaturated carboxylic acid (a) with a copolymer of the compound (c) having an epoxy group and an unsaturated double bond and the compound (b) having an unsaturated double bond. A carboxyl group-containing photosensitive resin obtained by reacting a saturated or unsaturated polybasic acid anhydride (d) with a hydroxyl group of
(4) A compound of an acid anhydride (e) having an unsaturated double bond and a compound (b) having an unsaturated double bond is reacted with a compound (f) having a hydroxyl group and an unsaturated double bond. Carboxyl group-containing photosensitive resin obtained by
(5) Esterification reaction (total esterification or partial esterification) of the epoxy group of the polyfunctional epoxy compound (g) having at least two epoxy groups in one molecule and the carboxyl group of the unsaturated monocarboxylic acid (h) Carboxyl group-containing photosensitive resin obtained by reacting a saturated or unsaturated polybasic acid anhydride (d) with the generated hydroxyl group.
(6) An organic compound having one carboxyl group in one molecule and no ethylenic unsaturated bond in the epoxy group of the copolymer of the compound (b) having an unsaturated double bond and glycidyl (meth) acrylate A carboxyl group-containing resin obtained by reacting the acid (i) and reacting the generated secondary hydroxyl group with a saturated or unsaturated polybasic acid anhydride (d),
(7) a carboxyl group-containing resin obtained by reacting a hydroxyl group-containing polymer (j) with a saturated or unsaturated polybasic acid anhydride (d),
(8) A compound (c) having an epoxy group and an unsaturated double bond is further added to a carboxyl group-containing resin obtained by reacting a hydroxyl group-containing polymer (j) with a saturated or unsaturated polybasic acid anhydride (d). Carboxyl group-containing photosensitive resin obtained by reaction,
(9) Reacts with an epoxy group, a polyfunctional epoxy compound (g) having at least two epoxy groups in one molecule, an unsaturated monocarboxylic acid (h), at least two hydroxyl groups in one molecule. Carboxyl group-containing photosensitivity obtained by reacting a reaction product (I) with a compound (k) having one other reactive group other than a hydroxyl group with a saturated or unsaturated polybasic acid anhydride (d). resin,
(10) An unsaturated group-containing polycarboxylic acid urethane comprising a reaction product of the reaction product (I), a saturated or unsaturated polybasic acid anhydride (d), and an unsaturated group-containing monoisocyanate (m). resin,
(11) A polyfunctional oxetane compound (n) having at least two oxetane rings in one molecule is reacted with an unsaturated monocarboxylic acid (h) and saturated with respect to the primary hydroxyl group in the resulting modified oxetane resin or A carboxyl group-containing photosensitive resin obtained by reacting an unsaturated polybasic acid anhydride (d),
(12) Obtained by introducing an unsaturated double bond into the reaction product of the bisepoxy compound (p) and the dicarboxylic acid (q) and subsequently reacting with the saturated or unsaturated polybasic acid anhydride (d). Carboxyl group-containing resin,
(13) Obtained by introducing an unsaturated double bond into the reaction product of the bisepoxy compound (p) and the bisphenol (r) and subsequently reacting with a saturated or unsaturated polybasic acid anhydride (d). A carboxyl group-containing resin, and (14) a reaction product of a novolak-type phenol resin (s) and an alkylene oxide (t) with an unsaturated monocarboxylic acid (h), and the resulting reaction product is saturated or unsaturated. A carboxyl group-containing photosensitive resin obtained by reacting a saturated polybasic acid anhydride (d).

  The carboxyl group-containing resin (1) includes an unsaturated carboxylic acid (a) such as acrylic acid and methacrylic acid, and an unsaturated double bond such as styrene, α-methylstyrene, lower alkyl (meth) acrylate, and isobutylene. On the other hand, the carboxyl group-containing photosensitive resin (2) is a copolymer of the unsaturated carboxylic acid (a) and the compound (b) having an unsaturated double bond. Ethylenically unsaturated groups such as vinyl groups, allyl groups, acryloyl groups, methacryloyl groups, and epoxy groups in a proportion that improves photocurability to such an extent that a sufficient photocuring depth can be obtained in part of the carboxyl groups of the coalescence , A resin having a reactive group such as acid chloride, such as glycidyl (meth) acrylate, reacted and an unsaturated double bond of the compound introduced into the side chain. Since a part of the carboxyl group of the unsaturated carboxylic acid (a) which is one monomer component of the copolymer remains unreacted, the resulting carboxyl group-containing photosensitive resin is soluble in an aqueous alkali solution. It is. Therefore, a film formed from a composition containing such a resin can be stably developed with an alkaline aqueous solution after selective exposure. In this specification, (meth) acrylate is a general term for acrylate and methacrylate, and the same applies to other similar expressions.

  The carboxyl group-containing photosensitive resin (3) includes a compound (c) having an epoxy group and an unsaturated double bond in the molecule, such as glycidyl (meth) acrylate, α-methylglycidyl (meth) acrylate, and the like. The carboxyl group of the unsaturated carboxylic acid (a) is added to the epoxy group of the copolymer of the compound (b) having an unsaturated double bond at a ratio that improves the photocurability to such an extent that a sufficient photocuring depth can be obtained. A group is reacted, an unsaturated double bond of the unsaturated carboxylic acid is introduced into a side chain, and a secondary hydroxyl group formed by the addition reaction is added to a polybasic acid anhydride (d), for example, phthalic anhydride, It is a resin in which tetrahydrophthalic anhydride, hexahydrophthalic anhydride or the like is esterified to introduce a carboxyl group into the side chain.

  The carboxyl group-containing photosensitive resin (4) includes an acid anhydride (e) having an unsaturated double bond, such as maleic anhydride, itaconic anhydride, and the compound (b) having the unsaturated double bond. A compound (f) having a hydroxyl group and an unsaturated double bond, such as hydroxy, in such a ratio that the photocurability is improved to such a degree that a sufficient photocuring depth can be obtained at a part of the acid anhydride group of the copolymer. Alkyl (meth) acrylates, monomers obtained by reacting (meth) acrylate with caprolactone, hydroxyl groups such as macromonomers obtained by reacting (meth) acrylate with polycaprolactone oligomers are reacted to form a half ester, and the compound (f) It is a resin in which an unsaturated double bond is introduced into the side chain.

  The carboxyl group-containing photosensitive resin (5) is a known conventional epoxy such as bisphenol A type, bisphenol F type, bisphenol S type, phenol novolac type, cresol novolac type, biphenol type, bixylenol type, N-glycidyl type and the like. The carboxyl group of the unsaturated monocarboxylic acid (h) such as (meth) acrylic acid is reacted with the epoxy group of the compound (g) at such a ratio that the photocurability is improved to such an extent that a sufficient photocuring depth can be obtained. For example, it is a resin in which an epoxy acrylate is produced and the secondary hydroxyl group produced by the addition reaction is esterified with the polybasic acid anhydride (d) to introduce a carboxyl group into the side chain. Such a carboxyl group-containing photosensitive resin is excellent in photocurability, and the backbone polymer epoxy acrylate exhibits hydrophobicity. Therefore, when the photocurable composition containing the resin is used, the hydrophobicity of the epoxy acrylate is advantageously used, and the development resistance of the deep part of the pattern which is difficult to be photocured is improved. As a result, the margin for setting conditions in the development and exposure processes is increased.

  The carboxyl group-containing resin (6) includes the compound (b) having an unsaturated double bond and having no hydroxyl group or acidic group, such as alkyl (meth) acrylate, substituted or unsubstituted styrene, and glycidyl (meta ) An organic acid (i) having one carboxyl group in one molecule and no ethylenically unsaturated bond in the glycidyl group of a copolymer having an acrylate main chain, for example, an alkylcarboxylic acid having 2 to 17 carbon atoms It is a resin obtained by reacting an acid, an aromatic group-containing alkylcarboxylic acid or the like, and adding the polybasic acid anhydride (d) to the generated secondary hydroxyl group. The introduction of a carboxyl group in this resin is produced by reacting an organic acid with the pendant glycidyl group of the above copolymer, and a polybasic acid anhydride is added to a secondary hydroxyl group located near the main chain. Therefore, the carboxyl group is bonded to a site near the main chain of the side chain, and contact with the basic inorganic fine particles is controlled by the steric hindrance between the main chain and the side chain. As a result, a composition containing such an alkali-soluble carboxyl group-containing resin together with an inorganic filler exhibits excellent storage stability, and hardly changes in viscosity or gels during storage.

  The carboxyl group-containing resin of the above (7) is a hydroxyl group-containing polymer (j) such as olefinic hydroxyl group-containing polymer, acrylic polyol, rubber polyol, polyvinyl acetal, styrene allyl alcohol resin, celluloses, etc. It is a resin in which a carboxyl group is introduced by reacting the relatively weak polybasic acid anhydride (d). Since such a carboxyl group-containing resin has a hydrophilic group (carboxyl group, hydroxyl group), it exhibits good wettability with respect to the substrate, and the photocurable composition containing this has a drying, exposure, and development step. Shows stable adhesion to the substrate and good storage stability.

  On the other hand, the carboxyl group-containing photosensitive resin of the above (8) is a ratio of improving the photocurability to such an extent that a sufficient photocuring depth can be obtained for the carboxyl group of the carboxyl group-containing resin (7). It is a resin obtained by reacting an epoxy group of a compound (c) having an unsaturated double bond with the group and introducing the unsaturated double bond of the compound (c) into a side chain. Such a carboxyl group-containing photosensitive resin is excellent in photocurability and exhibits a sufficient photocuring depth.

In the synthesis reaction of the carboxyl group-containing photosensitive resin (9), the polyfunctional epoxy compound (g) is reacted with an unsaturated monocarboxylic acid (h) (or compound (k)), and then the compound (k) (or There are a first method of reacting unsaturated monocarboxylic acid (h)) and a second method of reacting polyfunctional epoxy compound (g), unsaturated monocarboxylic acid (h) and compound (k) simultaneously. . Either method may be used, but the second method is preferable.
Specific examples of the compound (k) having at least two or more hydroxyl groups and one other reactive group (for example, carboxyl group, secondary amino group, etc.) other than the hydroxyl group that reacts with the epoxy group in one molecule. Examples thereof include polyhydroxy-containing monocarboxylic acids such as dimethylolpropionic acid, dimethylolacetic acid, dimethylolbutyric acid, dimethylolvaleric acid, and dimethylolcaproic acid; dialkanolamines such as diethanolamine and diisopropanolamine.

On the other hand, in the synthesis reaction of the unsaturated group-containing polycarboxylic acid urethane resin of (10), the reaction product (I) is reacted with the polybasic acid anhydride (d), and then the unsaturated group-containing polyresin produced is reacted. It is preferable to react the unsaturated group-containing monoisocyanate (m) with the hydroxyl group in the carboxylic acid resin.
Specific examples of the unsaturated monoisocyanate (m) include, for example, methacryloyl isocyanate, methacryloyloxyethyl isocyanate, organic diisocyanates (for example, tolylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate) and the above one molecule. Examples thereof include reaction products obtained by reacting (meth) acrylates having one hydroxyl group in an equimolar ratio.

  The carboxyl group-containing photosensitive resin of the above (11) uses a compound having an oxetane ring as a starting material instead of an epoxy resin that mainly generates a secondary hydroxyl group by reaction with an unsaturated monocarboxylic acid, and uses a polyfunctional oxetane. By reacting the unsaturated monocarboxylic acid (h) with the compound (n), and further reacting the primary hydroxyl group of the resulting modified oxetane resin with the polybasic acid anhydride (d), the bonding site is heated. It is a resin that is not easily cut and has excellent thermal stability. By using this carboxyl group-containing photosensitive resin, it is an alkali development type photo-curing and thermosetting composition that has excellent heat resistance and thermal stability. Can be prepared.

  The carboxyl group-containing resins (12) and (13) are bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, brominated bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, biphenol. -Type epoxy resin, bis-epoxy compound such as bixylenol-type epoxy resin (p), dicarboxylic acid (q) such as oxalic acid, malonic acid, succinic acid, phthalic acid, isophthalic acid, or bisphenols such as bisphenol A and bisphenol F An unsaturated double bond is introduced into the reaction product with (r), and then the polybasic acid anhydride (d) is further reacted with the secondary hydroxyl group produced by the above reaction or the remaining hydroxyl group. Thus, the resin is excellent in thermal stability. The introduction of unsaturated double bonds generally involves reacting the ethylenically unsaturated group such as vinyl group, allyl group, acryloyl group, methacryloyl group, etc. with the remaining hydroxyl group, carboxyl group, etc. in the above reaction or the generated hydroxyl group. This is carried out by reacting a compound having a reactive group such as an epoxy group or acid chloride.

  The carboxyl group-containing photosensitive resin (14) is excellent in flexibility and elongation due to chain extension by addition reaction of alkylene oxide (t) of novolak type phenol resin (s), and is generated by addition reaction of alkylene oxide. An unsaturated monocarboxylic acid (h) and a polybasic acid anhydride (d) are added to the terminal hydroxyl group, and there is no unsaturated group or carboxyl group on the same side chain, and each side chain Therefore, it is excellent in reactivity and has excellent alkali developability due to the presence of a terminal carboxyl group away from the main chain. Moreover, since the resin does not have or has only a slight hydrophilic alcoholic hydroxyl group, such as an acid anhydride modified resin of epoxy acrylate, it has excellent moisture absorption resistance. . Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, trimethylene oxide, tetrahydrofuran, and tetrahydropyran.

The carboxyl group-containing resin and the carboxyl group-containing photosensitive resin as described above may be used alone or in combination, but in any case, these are 10 to 80% by mass of the total amount of the composition, preferably 20 in total. It is preferable to mix | blend in the ratio of -60 mass%.
The carboxyl group-containing resin and the carboxyl group-containing photosensitive resin each have an acid value of 30 to 250 mgKOH / g, preferably 50 to 200 mgKOH / g, and in the case of a carboxyl group-containing photosensitive resin, its double bond equivalent. 350 to 2,000, preferably 400 to 1,500 can be suitably used. When the acid value of the resin is lower than 30 mgKOH / g, it is difficult for a sufficient curing reaction with the oxetane compound (B) to proceed, and it is also included as a film-forming component of the photocurable / thermosetting composition. If it is higher than 250 mgKOH / g, the adhesion of the film may be deteriorated or the photocured part (exposed part) may be dissolved during development. Since it occurs, it is not preferable. Further, in the case of a carboxyl group-containing photosensitive resin, it is preferable that the double bond equivalent of the photosensitive resin is larger than 2,000 because the work margin during development is narrow and a high exposure amount is required during photocuring. Absent.

（式中、Ｒ¹は水素原子又は炭素数１〜６のアルキル基である。）
アルキル基としては、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、ｓｅｃ−ブチル基、ｔ−ブチル基、ｎ−ペンチル基、イソペンチル基、ネオペンチル基、ｎ−ヘキシル基、イソヘキシル基等の直鎖又は分岐鎖のアルキル基が挙げられる。これらの中でも、３−ヒドロキシメチルオキセタン、３−メチル−３−ヒドロキシメチルオキセタン、３−エチル−３−ヒドロキシメチルオキセタンが好ましい。 As the oxetane compound (B), either a monofunctional oxetane compound having one oxetanyl group in the molecule or a polyfunctional oxetane compound having two or more oxetanyl groups in the molecule can be used. Although not limited, it is preferable to use a polyfunctional oxetane compound.
As the monofunctional oxetane compound, an oxetane compound represented by the following general formula (1) can be preferably used.

(In the formula, R ¹ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)
Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, t-butyl group, n-pentyl group, isopentyl group, neopentyl group, n-hexyl group, Examples thereof include a linear or branched alkyl group such as an isohexyl group. Among these, 3-hydroxymethyl oxetane, 3-methyl-3-hydroxymethyl oxetane, and 3-ethyl-3-hydroxymethyl oxetane are preferable.

上記一般式（２）において、Ｒ¹は前記と同じ意味であり、Ｒ²は、炭素数１〜１２の線状又は分岐状飽和炭化水素類、炭素数１〜１２の線状又は分岐状不飽和炭化水素類、下記式（Ａ）、（Ｂ）、（Ｃ）、（Ｄ）及び（Ｅ）で示される芳香族炭化水素類、式（Ｆ）及び（Ｇ）で示されるカルボニル基を含む直鎖状又は環状のアルキレン類、式（Ｈ）及び（Ｉ）で示されるカルボニル基を含む芳香族炭化水素類から選択される２つの原子価を持った基である。その他の２官能オキセタン化合物としては、カルド型、ナフタレン型などが挙げられる。 Examples of the bifunctional oxetane compound include bisoxetanes represented by the following general formula (2).

In the general formula (2), R ¹ has the same meaning as described above, and R ² represents a linear or branched saturated hydrocarbon having 1 to 12 carbon atoms, linear or branched non-carbon having 1 to 12 carbon atoms. Saturated hydrocarbons, aromatic hydrocarbons represented by the following formulas (A), (B), (C), (D) and (E), including carbonyl groups represented by formulas (F) and (G) It is a group having two valences selected from linear or cyclic alkylenes and aromatic hydrocarbons containing a carbonyl group represented by formulas (H) and (I). Examples of other bifunctional oxetane compounds include cardo type and naphthalene type.

式中、Ｒ³は、水素原子、炭素数１〜１２のアルキル基、アリール基、又はアラルキル基を表わし、Ｒ⁴は、−Ｏ−、−Ｓ−、−ＣＨ₂−、−ＮＨ−、−ＳＯ₂−、−ＣＨ（ＣＨ₃）−、−Ｃ（ＣＨ₃）₂−、又は−Ｃ（ＣＦ₃）₂−を表わし、Ｒ⁵は、水素原子又は炭素数１〜６のアルキル基を表わす。

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

式中、ｎは１〜１２の整数を表わす。

In the formula, n represents an integer of 1 to 12.

  Examples of the trifunctional oxetane compound include, in addition to the compound represented by the following general formula (3), hydroxyl groups such as oxetane and novolac resin, poly (hydroxystyrene), calixarene, or silicone resin such as silsesquioxane. An etherified product with a resin having In addition, a copolymer of an unsaturated monomer having an oxetane ring and an alkyl (meth) acrylate is also included.

上記一般式（３）において、Ｒ¹は前記と同じ意味であり、Ｒ⁶は、前記エーテル化物の水酸基含有樹脂残基、下記式（Ｊ）、（Ｋ）及び（Ｌ）で示されるような炭素数１〜１２の分岐状アルキレン基、式（Ｍ）、（Ｎ）及び（Ｐ）で示される芳香族炭化水素類である。また、ｍは残基Ｒ⁶に結合している官能基の数を表わし、３以上の整数、好ましくは３〜５０００の整数である。

In the general formula (3), R ¹ has the same meaning as described above, and R ⁶ represents a hydroxyl group-containing resin residue of the etherified product, as represented by the following formulas (J), (K), and (L). A branched alkylene group having 1 to 12 carbon atoms and aromatic hydrocarbons represented by formulas (M), (N) and (P). M represents the number of functional groups bonded to the residue R ⁶ and is an integer of 3 or more, preferably an integer of 3 to 5000.

式中、Ｒ⁷は、水素原子、炭素数１〜６のアルキル基、又はアリール基を表わす。

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

  The oxetane compound (B) as described above can be used alone or in combination of two or more, but in particular, a finely divided oxetane compound that is sparingly soluble in an organic solvent described later, or a soluble oxetane compound and a sparingly soluble oxetane compound. It is preferable to use a combination of oxetane compounds. The blending amount of the oxetane compound (B) as the thermosetting component is appropriately 5 to 200 parts by mass, preferably 15 to 100 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin (A). It is.

The present invention is characterized in that the acetylacetone metal complex (C) is used as a catalyst for the curing reaction between the carboxyl group-containing resin and the oxetane compound.
The metal used for forming a complex (complex salt) with acetylacetone belongs to groups 5 to 14 of the periodic table such as vanadium, chromium, manganese, iron, cobalt, nickel, titanium, copper, zinc, tin, zirconium, and aluminum. Although metals can be used, among them, vanadium, chromium, manganese, iron, cobalt, and nickel are preferable, and particularly preferable metals are manganese, iron, and cobalt.

  The amount of the acetylacetone metal complex (C) used is in the range of 0.1 to 25 mol%, preferably 0.5 to 20 mol%, more preferably 1 to 15 mol, relative to 1 mol of the oxetanyl group. %. When the amount of the acetylacetone metal complex (C) used is less than 0.1 mol% with respect to the oxetanyl group, the reaction hardly proceeds at a practical rate. Since the reaction promoting effect is not seen, it is not preferable in terms of economy.

  In addition to the components (A) to (C), the photocurable / thermosetting composition of the present invention includes a compound containing a polymerizable unsaturated double bond, a photopolymerizable monomer (D), and photopolymerization initiation. Contains agent (E). In the case where the carboxyl group-containing resin (A) is a carboxyl group-containing resin having no unsaturated double bond, the compound (D) containing a polymerizable unsaturated double bond is an essential component. On the other hand, in the case of a carboxyl group-containing photosensitive resin having an unsaturated double bond, photocuring is possible even if the compound (D) containing a polymerizable unsaturated double bond is not necessarily contained. Since it is difficult to obtain a curing depth, it is preferable to blend a compound (D) containing a polymerizable unsaturated double bond.

  Typical examples of the compound (D) containing a polymerizable unsaturated double bond include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, N-vinylpyrrolidone, acryloylmorpholine, methoxytetraethylene glycol acrylate, and methoxypolyethylene. Glycol acrylate, polyethylene glycol diacrylate, N, N-dimethylacrylamide, N-methylolacrylamide, N, N-dimethylaminopropylacrylamide, N, N-dimethylaminoethyl acrylate, N, N-dimethylaminopropyl acrylate, melamine acrylate, Diethylene glycol diacrylate, triethylene glycol diacrylate, propylene glycol diacrylate, dipropylene glycol diacrylate , Tripropylene glycol diacrylate, polypropylene glycol diacrylate, phenoxyethyl acrylate, tetrahydrofurfuryl acrylate, cyclohexyl acrylate, glycerin diglycidyl ether diacrylate, glycerin triglycidyl ether triacrylate, isobornyl acrylate, cyclopentadiene mono- or di- Acrylates, polyhydric alcohols such as hexanediol, trimethylolpropane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, tris-hydroxyethyl isocyanurate, or polyvalent acrylates of these ethylene oxide or propylene oxide adducts, and the above Each methacrylate corresponding to acrylate, polybasic Mono-, di-, tri-, or more polyesters of acid and hydroxyalkyl (meth) acrylate may be mentioned, and these may be used alone or in combination of two or more.

  The purpose of using the compound (D) containing the polymerizable unsaturated double bond is to dilute the carboxyl group-containing resin (A) to make it easy to apply and to impart photopolymerizability (unsaturated double bond). In the case of a carboxyl-containing resin that does not contain) or improvement (in the case of a carboxyl-containing photosensitive resin having an unsaturated double bond), the preferred amount used is 100 parts by mass of the carboxyl group-containing resin (A). It is the ratio of 3-50 mass parts with respect to. If the amount is less than 3 parts by mass, the effect of imparting or improving the photocurability is not sufficient.

  As the photopolymerization initiator (E), known compounds that generate radicals upon irradiation with active energy rays can be used, for example, acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy. 2-phenylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butyltrichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl]- Acetophenones such as 2-morpholino-propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, N, N-dimethylaminoacetophenone; benzophenone, methylbenzophenone Benzophenones such as 2-chlorobenzophenone, 4,4'-dichlorobenzophenone, 4,4'-bisdimethylaminobenzophenone, 4,4'-bisdiethylaminobenzophenone, Michler's ketone, 4-benzoyl-4'-methyldiphenyl sulfide; benzyl Benzoin ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; thioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, Thioxanthones such as 2,4-diethylthioxanthone and 2,4-diisopropylthioxanthone; 2-methylanthraquinone, 2-ethyl Anthraquinones such as luanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-aminoanthraquinone and 2,3-diphenylanthraquinone; organic peroxides such as benzoyl peroxide and cumene peroxide; 2,4,5 -Thiol compounds such as triarylimidazole dimer, riboflavin tetrabutyrate, 2-mercaptobenzoimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole; 2,4,6-tris-s-triazine, 2,2 , 2-tribromoethanol, tribromomethylphenylsulfone, and the like; 2,4,6-trimethylbenzoyldiphenylphosphine oxide and the like. Other examples include acridine compounds and oxime esters. These compounds can be used alone or in combination of two or more.

  Furthermore, the photopolymerization initiator (E) as described above includes N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, pentyl-4-dimethylaminobenzoate, triethylamine, triethanolamine. Tertiary amines such as β-thiodiglycol; sensitizing dyes such as (keto) coumarin and thioxanthene; and alkylboric acids such as cyanine, rhodamine, safranine, micalite green, and methylene blue It can be used in combination with one or more of photosensitizers or accelerators such as salts.

A preferable combination of the photopolymerization initiator (E) is 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one (for example, Irgacure 907 manufactured by Ciba Specialty Chemicals). ), 2-chlorothioxanthone (for example, Kayacure CTX manufactured by Nippon Kayaku Co., Ltd.), 2,4-diethylthioxanthone (for example, Kayacure DETX manufactured by Nippon Kayaku Co., Ltd.), 2-isopropylthioxanthone, 4-benzoyl-4 ′ -Combination with methyldiphenyl sulfide and the like.
Moreover, the suitable range of the usage-amount of the above photoinitiators (E) is 0.2-30 mass parts with respect to 100 mass parts of said carboxyl group-containing resin (A), Preferably it is 2-10 masses. This is the ratio of parts. When the blending ratio of the photopolymerization initiator is less than 0.2 parts by mass, the photo-curing property is deteriorated. Since it gets worse, it is not preferable.

In a preferred embodiment of the curable composition and the photocurable / thermosetting composition of the present invention, as described above, the component (F) contains an s-triazine compound and / or dicyandiamide. Examples of the s-triazine compound include melamine, guanamine, acetoguanamine, benzoguanamine, 2,4,6-triamino-S-triazine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2, 4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine / isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine / isocyanuric acid adduct, etc. Preferably, an s-triazine compound and / or dicyandiamide that also functions as an adhesion-imparting agent is used in combination with the acetylacetone metal complex (C) as the curing catalyst.
The compounding amount of the s-triazine compound and / or dicyandiamide is sufficient in a normal quantitative ratio, for example, 0.1 to 20 parts by mass, preferably 0. 0 to 100 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin (A). It is a ratio of 5 to 15.0 parts by mass.

  Furthermore, the curable composition and the photocurable / thermosetting composition of the present invention may contain an organic solvent as necessary. Examples of organic solvents include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene and xylene; cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol Glycol ethers such as monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monotyl ether; ethyl acetate, butyl acetate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, Propylene glycol monobutyl ether acetate, dipropylene glycol Acetic esters such as nomethyl ether acetate; Alcohols such as ethanol, propanol, ethylene glycol, and propylene glycol; Aliphatic hydrocarbons such as octane and decane; Petroleum such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha Examples thereof include a solvent, and can be used alone or in combination of two or more.

  The purpose of using the organic solvent is to dissolve the carboxyl group-containing resin (A) and other components, dilute it, apply it as a liquid on the substrate, and then temporarily dry it to form a film, or alternatively This is because a dry film can be formed by coating on a support film and then temporarily drying to form a film. The amount of the organic solvent used is not limited to a specific ratio, but a range of about 30 to 300 parts by mass is appropriate for 100 parts by mass of the carboxyl group-containing resin (A), and a coating method to be selected. It can be set appropriately according to.

Furthermore, in the curable composition and the photocurable / thermosetting composition of the present invention, a part of the thermosetting component is within a range not impairing the effect of using the oxetane compound (B) as the thermosetting component. An epoxy compound can also be mixed. As the epoxy compound, any compound having two or more epoxy groups in the molecule can be used. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, brominated bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, biphenol type epoxy resin, bixylenol type epoxy resin, alicyclic epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, brominated phenol novolak type epoxy resin, Glycidyl ether compounds such as bisphenol A novolac epoxy resin, glycidyl ether such as diglycidyl terephthalate, diglycidyl hexahydrophthalate, diglycidyl dimer Tellurium compounds, triglycidyl isocyanurate, N, N, N ′, N′-tetraglycidylmetaxylenediamine, N, N, N ′, N′-tetraglycidylbisaminomethylcyclohexane, N, N-diglycidylaniline, etc. Known and commonly used epoxy compounds such as glycidylamine compounds can be mentioned. These epoxy compounds can be used alone or in combination of two or more. As the epoxy compound, any epoxy compound that is hardly soluble or soluble in an organic solvent can be used, but from the viewpoint of developability and the like, it is a hardly soluble solid or semi-solid fine particulate epoxy compound or a soluble epoxy with this. Preference is given to using a mixture of compounds.
Furthermore, in order to accelerate the thermosetting reaction, a small amount of known epoxy curing accelerators such as quaternary ammonium salts, quaternary phosphonium salts, tertiary amines and imidazoles can be used in combination.

  In addition, the composition of the present invention has, as necessary, barium sulfate, barium titanate, silicon oxide powder, amorphous silica, talc, magnesium carbonate, calcium carbonate, for the purpose of improving properties such as adhesion and hardness. Known and commonly used inorganic fillers such as aluminum oxide, aluminum hydroxide, glass fiber, carbon fiber, mica powder and the like can be blended, and the blending ratio is suitably in the range of 0 to 60% by weight, preferably 5 to 5%. 40% by mass. Further, as required, known and commonly used colorants such as phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow, crystal violet, titanium oxide, carbon black, naphthalene black, hydroquinone, hydroquinone monomethyl ether, tert-butylcatechol , Known and conventional thermal polymerization inhibitors such as pyrogallol and phenothiazine, known and commonly used thickeners such as asbestos and fine silica, defoamers and / or leveling agents such as silicones, fluorines and polymers, thiazoles, Known and commonly used additives such as adhesion-imparting agents such as triazole and silane coupling agents can be blended.

  In the production of the dry film of the present invention, the curable composition of the present invention or the photocurable / thermosetting composition as described above is adjusted to a viscosity suitable for the coating method as necessary, and the conventional method is used. In the same manner as above, an appropriate support film, for example, a flexible base film having a film thickness of about 15 to 125 μm, such as polyethylene terephthalate (PET), polyethylene (PE), polypropylene (PP), polycarbonate, polyether sulfone, polyvinyl chloride, etc. The organic solvent contained in the composition at a temperature of, for example, about 60 to 140 ° C., generally about 120 ° C., after being applied so as to have a thickness of about 10 to 150 μm after drying. Is dried by volatilization to obtain a dry film having a dry film layer. The dry film layer formed on the support film is a release film having a film thickness of about 15 to 100 μm, such as a PET film, a PP film, a PE film, or a film coated or baked with silicone on this when not used. It is preferable to store a protective film having properties. The protective film is for stably protecting the dry film when not in use, and is removed during use. Further, in order to prevent the oxygen desensitizing action of the photocurable / thermosetting composition and to prevent the adhesion of the photomask for pattern formation that is in close contact during exposure, polyvinyl alcohol is further added on the dry film layer. A layer having a film thickness of about 1 to 10 μm of a water-soluble composition such as saponified polyvinyl acetate can be formed.

  The pattern forming method using the photocurable / thermosetting composition of the present invention will be explained. First, the viscosity is adjusted to a viscosity suitable for the coating method as necessary, and this is applied to, for example, a printed wiring board formed with a circuit. Apply by screen printing method, curtain coating method, dipping method, spray coating method, roll coating method, spin coating method, etc., and evaporate and dry the organic solvent contained in the composition at a temperature of about 60-100 ° C., for example. Thus, a tack-free coating film can be formed.

Then, the resist pattern is developed by selectively exposing with an actinic ray through a photomask having a pattern formed by a contact method or a non-contact method, and developing an unexposed portion with a dilute alkaline aqueous solution (for example, 0.5 to 5% sodium carbonate aqueous solution). Can be formed. Furthermore, for example, it is heated and cured at a temperature of about 140 to 200 ° C. Thereby, in addition to the curing reaction of the thermosetting component, through the acceleration of polymerization of the photocurable component and the copolymerization with the thermosetting component, the resulting resist film has heat resistance, solder adhesion resistance, solvent resistance, Various properties such as acid resistance, adhesion, electroless gold plating resistance, electrical properties, printability, and hardness can be improved.
Moreover, when using as an interlayer insulation layer (insulation layer between conductor circuit layers) of a build-up multilayer printed wiring board, a pattern can be similarly formed.

In the case of a photosensitive dry film having a protective film, the protective film is peeled off, the dry film layer is brought into close contact with the substrate to be patterned, the support film is peeled off, and the photocurable property is removed. Transfer the dry film layer made of the thermosetting composition. As the transfer method, a thermocompression bonding method in which the substrate to be treated is heated in advance is preferable. Alternatively, a vacuum pressure bonding method in which pressure bonding is performed under vacuum may be used. The substrate to be treated can be arbitrarily selected according to the purpose of using the photosensitive dry film, but when used as a solder resist for a printed wiring board, for example, it is transferred to a printed wiring board on which a circuit is formed in advance. Moreover, when using as an interlayer insulation layer of a buildup multilayer printed wiring board, it transfers to an inner layer board.
Thereafter, in the same manner as described above, the dried film layer after transfer is exposed through a pattern mask, then developed, and a pattern is formed by removing unexposed portions.

As the alkaline aqueous solution used for the above development, alkaline aqueous solutions such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, tetramethylammonium hydroxide, and organic amines are used. it can.
As the irradiation light source for photocuring, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a xenon lamp, a metal halide lamp, or the like is appropriate. In addition, a laser beam, an electron beam, etc. can also be utilized as exposure actinic rays.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the following examples are only for illustrating the present invention and do not limit the present invention. In the following description, “part” means “part by mass” unless otherwise specified.

Examples 1 to 16 and Comparative Examples 1 and 2:
The compounding components shown in Table 1 were mixed at the respective compounding ratios shown in Table 2, and kneaded using a three-roll mill to obtain a thermosetting composition.

Coating film production:
The thermosetting compositions of Examples 1 to 16 and Comparative Examples 1 and 2 were each applied to a copper-clad laminate with a thickness of 50 μm with an applicator and heated at 170 ° C. for 60 minutes to obtain a cured coating film. Got.

Performance evaluation:
(1) Curability:
The surface of the cured coating film was rubbed 50 times with absorbent cotton soaked with acetone, and the presence or absence of cloudiness on the surface was visually observed and evaluated according to the following criteria.
A: No change at all.
○: Almost no change.
Δ: Cloudy on the surface.
X: The coating film dissolved and reached the ground.

(2) Heat resistance:
The cured coating film was immersed in a solder bath at 260 ° C. for 10 seconds in accordance with the method of JIS C-6481, and then a peeling test using a cellophane adhesive tape was repeated three times. Judgment criteria are as follows.
A: No change in coating film.
○: The coating film has almost no change.
Δ: Some change is observed in the coating film.
X: The film peeled off.

(3) Pencil hardness:
It measured based on JIS K-5400.

(4) Gold plating resistance:
Using a commercially available electroless nickel plating bath and electroless gold plating bath, plating was performed under conditions of nickel 3 μm and gold 0.03 μm, and the surface state of the cured coating film was observed. Judgment criteria are as follows.
A: No change at all.
○: There is almost no change.
(Triangle | delta): The thing from which peeling or cloudiness produced.
X: Remarkably peeled off or clouded.

表３に示される結果から明らかなように、カルボキシル基含有樹脂とオキセタン化合物を含む硬化反応系の触媒としてアセチルアセトン金属錯体を用いると、良好な硬化塗膜が得られる。これに対し、硬化触媒としてテトラフェニルホスホニウムブロミドを添加した比較例１の場合、及びメラミンを用いた比較例２の場合、硬化性、耐熱性、鉛筆硬度、金めっき耐性共に劣っていた。また、実施例１５及び１６の結果から、硬化性組成物がｓ−トリアジン化合物である金めっき耐性がより一層向上することがわかる。 The results are shown in Table 3.

As is apparent from the results shown in Table 3, when an acetylacetone metal complex is used as a catalyst for a curing reaction system containing a carboxyl group-containing resin and an oxetane compound, a good cured coating film can be obtained. In contrast, in the case of Comparative Example 1 in which tetraphenylphosphonium bromide was added as a curing catalyst and in the case of Comparative Example 2 using melamine, the curability, heat resistance, pencil hardness and gold plating resistance were all inferior. Moreover, it turns out that the gold-plating tolerance whose curable composition is a s-triazine compound improves further from the result of Example 15 and 16.

Next, examples relating to the photocurable / thermosetting composition will be described.
Preparation of photosensitive resin solution:
Synthesis example 1:
A cresol novolac type epoxy resin (Epiclon N-695, manufactured by Dainippon Ink & Chemicals, Inc., epoxy equivalent 220 g / eq) (220 parts) was placed in a four-necked flask equipped with a stirrer and a reflux condenser, and carbitol acetate 214 was added. Part was added and dissolved by heating. Next, 0.1 part of hydroquinone as a polymerization inhibitor and 2.0 parts of triphenylphosphine as a reaction catalyst were added. This mixture was heated to 95 to 105 ° C., and 72 parts of acrylic acid was gradually added dropwise to react for 16 hours. The reaction product was cooled to 80 to 90 ° C., 106 parts of tetrahydrophthalic anhydride was added, allowed to react for 8 hours, cooled and taken out. Thus, a photosensitive resin having both an ethylenically unsaturated bond and a carboxyl group was obtained as a photosensitive resin solution having a nonvolatile content of 65% and a solid content acid value of 100 mgKOH / g. Hereinafter, this photosensitive resin solution is referred to as A-1 varnish.

Synthesis example 2:
After dissolving 380 parts of bisphenol F type epoxy compound (epoxy equivalent 950 g / eq, softening point 85 ° C.) having an average polymerization degree n of 6.2 and 925 parts of epichlorohydrin in 462.5 parts of dimethyl sulfoxide, At 70 ° C., 98.5% NaOH was added over 60.9 parts (1.5 mol) over 100 minutes. After the addition, the reaction was further carried out at 70 ° C. for 3 hours. After completion of the reaction, 250 parts of water was added and washed with water. After the oil / water separation, most of the dimethyl sulfoxide and excess unreacted epichlorohydrin are recovered by distillation under reduced pressure from the oil layer, then the dimethyl sulfoxide is distilled off, and the reaction product containing the by-product salt is dissolved in 750 parts of methyl isobutyl ketone, Further, 10 parts of 30% NaOH was added and reacted at 70 ° C. for 1 hour. After completion of the reaction, washing was performed twice with 200 parts of water. After separation of oil and water, methyl isobutyl ketone was recovered by distillation from the oil layer to obtain an epoxy resin having an epoxy equivalent of 310 g / eq and a softening point of 69 ° C. When the epoxy resin obtained was calculated from the epoxy equivalent, about 5 out of 6.2 alcoholic hydroxyl groups in the starting material bisphenol F type epoxy compound were epoxidized. 310 parts of this epoxy resin and 251 parts of carbitol acetate were charged, heated to 90 ° C. and dissolved. The resulting solution was cooled to 60 ° C., 60 parts of acrylic acid, 97 parts of dimer acid (acid value 196 mg KOH / g), 0.8 parts of methylhydroquinone and 2.5 parts of triphenylphosphine were added and heated at 80 ° C. The resultant was dissolved and reacted at 98 ° C. for 35 hours to obtain an epoxy acrylate having an acid value of 0.5 mg KOH / g and a solid content of 65%. Next, 718.5 parts of this epoxy acrylate, 100 parts of succinic anhydride, and 54 parts of carbitol acetate were added and reacted at 90 ° C. for 6 hours. The photosensitivity was such that the solid content acid value was 99 mgKOH / g and the solid content was 65%. A resin solution was obtained. Hereinafter, this photosensitive resin solution is referred to as A-2 varnish.

Examples 17-21
The blending components shown in Table 4 were mixed at the blending ratios shown in Table 5, and kneaded using a three-roll mill to obtain a photocurable / thermosetting composition.

Each of the photocurable and thermosetting compositions of Examples 17 to 19 was applied to a printed wiring board formed with a circuit so as to have a film thickness of about 20 μm by screen printing, and then heat-dried at 80 ° C. for 30 minutes. I let you. Thereafter, these substrates were exposed through a negative film at an exposure amount of 300 mJ / cm ² . Subsequently, development was performed with a 1 wt% sodium carbonate aqueous solution for 60 seconds to form an image. Next, a thermosetting reaction was performed at 170 ° C. for 60 minutes to prepare a test substrate.

Performance evaluation:
(1) Developability:
Residues were evaluated by visually observing the coating after development in the coating preparation process.
○: No residue at all.
Δ: Some residue.
X: The thing with a residue.

(2) Sensitivity:
Using UGRA PLATE CONTROL WEGI as a negative film in the coating film production process, the number of steps of the developed step tablet was visually confirmed.

(3) Storage stability:
The compositions of Examples 17 to 19 were put into an oven at 50 ° C., and the viscosity change rate after 5 days was evaluated. Judgment criteria are as follows.
○: Change rate of viscosity is less than 30%.
Δ: Viscosity change rate of 30 to 50%.
X: Viscosity change rate exceeds 50%.

(4) Heat resistance:
The cured coating film was immersed in a solder bath at 260 ° C. for 10 seconds in accordance with the method of JIS C-6481, and then a peeling test using a cellophane adhesive tape was repeated three times. Judgment criteria are as follows.
○: No change in coating film.
Δ: Some change is observed in the coating film.
X: The film peeled off.

(5) Acid resistance:
The cured coating film was immersed in a 10 wt% sulfuric acid aqueous solution at 25 ° C. for 10 minutes, and then subjected to a peeling test using a cellophane adhesive tape. Judgment criteria are as follows.
A: No change at all.
○: There is almost no change.
Δ: Some change is observed in the coating film.
X: The film peeled off.

(6) Alkali resistance:
The cured coating film was immersed in a 10 wt% sodium hydroxide aqueous solution at 25 ° C. for 10 minutes and then subjected to a peeling test using a cellophane adhesive tape. Judgment criteria are as follows.
○: No change in coating film.
Δ: Some change is observed in the coating film.
X: The film peeled off.

(7) Solvent resistance:
The cured coating film was immersed in propylene glycol monomethyl ether acetate at 25 ° C. for 10 minutes and then subjected to a peeling test using a cellophane adhesive tape. Judgment criteria are as follows.
○: No change in coating film.
Δ: Some change is observed in the coating film.
X: The film peeled off.

(8) Pencil hardness:
It measured based on JIS K-5400.

(9) Gold plating resistance:
Using a commercially available electroless nickel plating bath and electroless gold plating bath, plating was performed under conditions of nickel 3 μm and gold 0.03 μm, and the surface state of the cured coating film was observed. Judgment criteria are as follows.
A: No change at all.
○: There is almost no change.
(Triangle | delta): The thing from which peeling or cloudiness produced.
X: Those with significant peeling or cloudiness

表６に示される結果から、本発明の各実施例によれば、組成物は１液で充分な保存安定性があり、ソルダーレジストとして十分な特性がある塗膜が得られることが明らかである。 The test results are summarized in Table 6.

From the results shown in Table 6, it is clear that according to each example of the present invention, the composition has sufficient storage stability with one liquid and a coating film having sufficient characteristics as a solder resist can be obtained. .

Next, the formation of a dry film will be described.
The compositions of Examples 20 and 21 were diluted with methyl ethyl ketone to adjust the viscosity to 20 dPa · s. Thereafter, a dry film having a thickness of 50 μm was produced on the PET film by a conventional method. This was laminated on a printed wiring board on which a circuit was formed, and was exposed through a negative film with an exposure amount of 300 mJ / cm ² . Next, after the PET film was peeled off, development was performed with a 1 wt% sodium carbonate aqueous solution for 60 seconds to form an image. Next, a thermosetting reaction was performed at 170 ° C. for 60 minutes to prepare a test substrate.

About the obtained test substrate, developability, sensitivity, storage stability, heat resistance, acid resistance, alkali resistance, solvent resistance, pencil hardness, and gold plating resistance were evaluated in the same manner as described above. However, the storage stability and gold plating resistance were evaluated by changing the measurement conditions as follows.
(3) Storage stability:
The prepared dry film was stored in a dark place at 25 ° C. for 6 months, then laminated on a copper-clad laminate, the PET film was peeled off, and then developed with a 1 wt% sodium carbonate aqueous solution for 60 seconds to check for residues. Was visually evaluated.
○: No residue at all.
Δ: Some residue.
X: The thing with a residue.

(9) Resistance to gold plating Using a commercially available electroless nickel plating bath and electroless gold plating bath, plating was performed under the conditions of 3 μm nickel and 0.03 μm gold, and the surface state of the cured coating film was observed. Judgment criteria are as follows.
A: No change at all.
○: There is almost no change.
(Triangle | delta): The thing from which peeling or cloudiness produced.
X: Remarkably peeled off or clouded.

表７に示される結果から明らかなように、本発明の実施例２０、２１によれば、充分な保存安定性があり、ソルダーレジストとして充分な特性を有するドライフィルムが得られた。
The test results are summarized in Table 7.

As is clear from the results shown in Table 7, according to Examples 20 and 21 of the present invention, a dry film having sufficient storage stability and sufficient characteristics as a solder resist was obtained.

Claims (6)

A curable composition comprising (A) a carboxyl group-containing resin, (B) a compound having an oxetanyl group, and (C) an acetylacetone metal complex. (A) a carboxyl group-containing resin, (B) a compound having an oxetanyl group, (C) an acetylacetone metal complex, (D) a compound containing a polymerizable unsaturated double bond, and (E) a photopolymerization initiator, A curable composition characterized by being photocurable and thermosetting. Furthermore, (F) s-triazine compound and / or dicyandiamide are contained, The curable composition of Claim 1 or 2 characterized by the above-mentioned. The curable composition according to claim 1, wherein the curable composition is in the form of a dry film. Hardened | cured material obtained by hardening | curing the curable composition as described in any one of the said Claims 1 thru | or 4. A printed wiring board, wherein a solder resist and / or an insulating layer between conductor circuit layers is formed of a cured product of the curable composition according to any one of claims 1 to 4.