JP4814135B2 - Curable composition and cured product thereof - Google Patents

Description

  The present invention relates to a curable composition used in the production of printed wiring boards and the like. More specifically, the present invention is excellent in storage stability, can be composed in a one-pack type, and has crack resistance, electrical insulation, PCT. (Pressure Cooker Test) relates to a photocurable and thermosetting composition that gives a cured product having excellent properties such as resistance, adhesion, solder heat resistance, chemical resistance, and electroless gold plating resistance, and the cured product .

Currently, curable resin compositions that are used as resists for printed wiring boards are mainly alkali-developing curable compositions that use dilute aqueous alkali solutions as developing solutions in consideration of environmental problems.
As such an alkali development type curable composition, for example, a curable resin obtained by adding a polybasic acid anhydride to a reaction product of a novolak type epoxy compound and an unsaturated monocarboxylic acid, a photopolymerization initiator, Composition comprising a photopolymerizable monomer and a polyfunctional epoxy resin having two or more epoxy groups in one molecule on the market (see Patent Document 1), a polyfunctional epoxy compound, and a phenol compound having a hydroxyl group-containing substituent And a photosensitive prepolymer obtained by reacting a reaction product of an unsaturated group-containing monocarboxylic acid with a polybasic acid anhydride, a photopolymerization initiator, a photosensitive (meth) acrylate compound, and a conventional commercially available polyfunctional epoxy. A composition comprising a resin and a curing catalyst (see Patent Document 2), an aromatic epoxy resin having two glycidyl groups in one molecule and one molecule Epihalohydrin is reacted with an alcoholic secondary hydroxyl group obtained by reacting with an aromatic alcohol resin having two phenolic hydroxyl groups, and the resulting reaction product is unsaturated group-containing monocarboxylic acid, then acid anhydride A composition comprising a curable resin obtained by adding a photopolymerization initiator, a photopolymerization initiator, a conventional commercially available polyfunctional epoxy resin or a photosensitive (meth) acrylate compound (see Patent Documents 3 and 4), novolak Carboxyl group-containing photosensitive resin obtained by reacting an unsaturated group-containing monocarboxylic acid with the reaction product of a phenolic resin and an alkylene oxide, and reacting the resulting reaction product with a polybasic acid anhydride, photopolymerization A curable composition containing an initiator, a conventional commercially available polyfunctional epoxy resin, or a photosensitive (meth) acrylate compound (for example, Patent Document 5 reference), and the like.

  As described above, several composition systems have been proposed as curable compositions, and are currently used in large quantities in the production of actual printed wiring boards. However, in order to improve solder heat resistance etc., the conventional curable composition usually contains a polyfunctional epoxy resin having two or more epoxy groups as a thermosetting component. However, since this polyfunctional epoxy resin has high reactivity, the curable composition containing it has a short shelf life (preservation life) and tends to thicken before application to a circuit board blank. Difficult to compose into mold. Therefore, in general, a two-part composition of a curing agent solution mainly composed of a polyfunctional epoxy resin and a main agent solution mainly composed of a photosensitive prepolymer and blended with a curing accelerator is mixed, and these are mixed in use. There was a problem in terms of workability.

  Recently, from the viewpoint of processability and smoothness of the cured film surface, it has been required to form a solder resist in a dry film. However, when the curable 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. Therefore, at present, most solder resist dry films need to be stored at 0 ° C. or less, and there is a problem that it takes time for transportation and storage.

As a method for solving such a problem, a curable composition containing an unsaturated group-containing polycarboxylic acid resin, a diluent, a photopolymerization initiator, and an allyl nadiimide compound (see Patent Document 6) or A curable composition comprising a compound having a carboxyl group, an ethylenically unsaturated compound, a compound having two or more epoxy groups in one molecule, a latent epoxy curing agent, and a photopolymerization initiator ( Patent Document 7) has been proposed. However, none of these have yet satisfied both the storage stability and various properties required for solder resist.
JP 61-243869 (Claims, page 3, lower left column, line 10 to page 4, upper left column, line 5; page 4, lower left column, lines 12 to 19) JP 11-288091 A (claims, paragraph [0024]) JP-A-5-32746 (Claims, paragraphs [0076] to [0079]) International Publication WO 01 / 53375A1 (Claims) International Publication WO 02/024774 A1 (Claims) JP-A-9-278849 (Claims) JP-A-3-191352 (Claims)

  The present invention has been made in view of the above-described problems of the prior art, and its purpose is excellent in storage stability, can be composed in a one-pack type, and has crack resistance, electrical insulation, PCT. (Pressure Cooker Test) To provide a curable composition capable of obtaining an excellent cured film sufficiently satisfying characteristics such as resistance, adhesion, solder heat resistance, chemical resistance, and electroless gold plating resistance. .

In order to achieve the above object, according to the present invention, (A) an aldehyde is partially subjected to an addition reaction with an epoxy resin having two or more epoxy groups in one molecule (hereinafter referred to as a polyfunctional epoxy resin). Curability characterized in that it contains an epoxy resin having a 1,3-dioxolane ring, (B) a carboxyl group-containing compound, (C) a photosensitive (meth) acrylate compound and (D) a photopolymerization initiator. A composition is provided.
According to another aspect of the present invention, (A) an epoxy resin having a 1,3-dioxolane ring, obtained by partially adding an aldehyde to the polyfunctional epoxy resin, (B ′) a carboxyl group There is provided a curable composition containing the photosensitive compound and (D) a photopolymerization initiator.
According to a preferred embodiment, in the epoxy resin (A), the reaction ratio of the aldehyde to the polyfunctional epoxy resin is 0.03 to 0.9 equivalent of the carbonyl group with respect to 1 equivalent of the epoxy group.

The curable composition may be in a liquid form or a so-called dry film.
Therefore, according to another aspect of the present invention, there is provided a film comprising a support and a layer made of the curable composition formed on the support. According to the suitable aspect of this invention, the film provided with the cover film which can be peeled further on the curable composition layer of the said film is provided.
According to still another aspect of the present invention, a cured product obtained by using the curable composition is provided.

Since the curable composition of the present invention uses an epoxy resin (A) having a 1,3-dioxolane ring instead of a conventionally used polyfunctional epoxy resin, it has excellent storage stability and is a one-part solution. And the epoxy resin (A) together with the carboxyl group-containing compound (B) and the photosensitive (meth) acrylate compound (C), or the carboxyl group-containing photosensitive compound (B ′), and Because it contains a photopolymerization initiator (D), it is photocurable and thermosetting, and it requires electrical insulation, PCT resistance, etc. required for resists that can be used for high-density printed wiring boards and surface mounting. And a cured film excellent in crack resistance, adhesion, heat resistance, chemical resistance, electroless plating resistance, and the like can be obtained.
Moreover, since the said (B) component or (B ') component has a carboxyl group, the coating film can be developed with aqueous alkali solution. Furthermore, since it is excellent in storage stability, can be composed in a one-pack type, and can produce a photosensitive dry film excellent in storage stability at room temperature, it is advantageous in terms of workability.

  As a result of intensive studies to solve the above-mentioned problems, the present inventor has obtained an epoxy resin (A) having a 1,3-dioxolane ring, which is obtained by partially adding an aldehyde to a polyfunctional epoxy resin. An epoxy resin (A) having a 1,3-dioxolane ring in which a carbonyl group is 0.03 to 0.9 equivalents relative to 1 equivalent of an epoxy group, and a carboxyl group-containing aldehyde reaction ratio with respect to a polyfunctional epoxy resin The combination with the compound (B and / or B ′) is superior in storage stability compared to the combination of a polyfunctional epoxy resin and a carboxyl group-containing compound generally used conventionally, and in addition to these, it is photosensitive. The cured product of the composition containing the (meth) acrylate compound (C) and the photopolymerization initiator (D) is an ordinary polyfunctional epoxy resin, carboxyl group Compared with a cured product of a composition comprising an organic compound (B and / or B ′), a photosensitive (meth) acrylate compound (C) and a photopolymerization initiator (D), it is not inferior in heat resistance and is flexible. The inventors have found that the film is formed, has excellent adhesion to the base material, and has the above-described excellent characteristics necessary as a resist, and the present invention has been completed.

  That is, the epoxy resin (A) having a 1,3-dioxolane ring obtained by partially adding an aldehyde to the polyfunctional epoxy resin contained in the curable composition of the present invention is, for example, an aldehyde for the epoxy resin. When the carbonyl group is 0.03 to 0.9 equivalent with respect to 1 equivalent of the epoxy group, the 1,3-dioxolane ring formed by the reaction between the unreacted epoxy group and the epoxy group and the aldehyde It has a structure with (However, the reaction with an acid catalyst used in the reaction, for example, the reaction of phosphoric acid with an epoxy group may produce a small amount of phosphate ester.) This 1,3-dioxolane ring is a normal curing agent. Under the conditions, the ring hardly opens and reacts with the carboxyl group. Therefore, the reactivity of the obtained epoxy resin having a 1,3-dioxolane ring and a carboxyl group-containing compound is lowered by the presence of the 1,3-dioxolane ring, and even when these coexist, the original ( Compared to the case of using a normal polyfunctional epoxy resin, the storage stability is excellent. However, since a sufficient amount of epoxy groups are present, the cured coating film obtained by the reaction between the epoxy resin having a 1,3-dioxolane ring and the carboxyl group-containing compound is the same as the original (normal) polyfunctional epoxy resin. It is not inferior to the cured coating film obtained by reaction with a carboxyl group-containing compound, and is excellent in various properties as described above.

  Therefore, together with an epoxy resin (A) having a 1,3-dioxolane ring obtained by partially adding an aldehyde to a polyfunctional epoxy resin, a carboxyl group-containing compound (B) and a photosensitive (meth) acrylate compound (C ), Or a curable composition containing a carboxyl group-containing photosensitive compound (B ′) and a photopolymerization initiator (D) is excellent in storage stability and can be composed in a one-pack type, and In addition to exhibiting excellent alkali developability, photocurability and / or thermosetting, selective exposure, development and finish curing of the coating film, crack resistance, electrical insulation, PCT resistance, adhesion, solder heat resistance A cured product having excellent properties, chemical resistance, electroless gold plating resistance, and the like can be obtained.

Hereinafter, the curable composition of the present invention will be described in detail.
First, the epoxy resin (A) having a 1,3-dioxolane ring used in the present invention can be easily obtained by partial addition reaction of a polyfunctional epoxy resin and an aldehyde using an acid as a catalyst. As for the reaction ratio of the aldehyde to the polyfunctional epoxy resin, the carbonyl group is 0.03 to 0.9 equivalent with respect to 1 equivalent of the epoxy group, preferably 0.05 to 0.8 equivalent, more preferably 0.8. 1 to 0.7 equivalent, particularly preferably 0.2 to 0.5 equivalent.

  Examples of the polyfunctional epoxy resin include JER828, JER834, JER1001, and JER1004 manufactured by Japan Epoxy Resins Co., Ltd., Epicron 840, Epicron 850, Epicron 1050, Epicron 1050, and Epitolon 2055 manufactured by Dainippon Ink & Chemicals, Inc. Epototo YD-011, YD-013, YD-127, YD-128 manufactured by Dow Chemical Co., Ltd. E. R. 317, D.E. E. R. 331, D.D. E. R. 661, D.D. E. R. 664, Sumitomo Chemical Co., Ltd. bisphenol A type epoxy resins such as Sumi-Epoxy ESA-011, ESA-014, ELA-115, ELA-128 (all trade names); manufactured by Japan Epoxy Resin Co., Ltd. JERYL903, Daikoku Ink Chemical Co., Ltd. Epicron 152, Epicron 165, Toto Kasei Co., Ltd. Epototo YDB-400, YDB-500, Dow Chemical Co., Ltd. E. R. 542, brominated epoxy resins such as Sumi-epoxy ESB-400 and ESB-700 (both trade names) manufactured by Sumitomo Chemical Co., Ltd .; JER152, JER154 and Dow Chemical Co., Ltd. manufactured by Japan Epoxy Resin Co., Ltd. D. E. N. 431, D.D. E. N. 438, Epicron N-730, Epicron N-770, Epicron N-865, manufactured by Dainippon Ink & Chemicals, Inc. Epototo YDCN-701, YDCN-704, manufactured by Tohto Kasei Co., Ltd., manufactured by Nippon Kayaku Co., Ltd. Novolak type epoxy such as EPPN-201, EOCN-1025, EOCN-1020, EOCN-104S, RE-306, Sumitomo Epoxy ESCN-195X, ESCN-220 (all trade names) manufactured by Sumitomo Chemical Co., Ltd. Resins; Bisphenol F such as Epicron 830 manufactured by Dainippon Ink & Chemicals, JER807 manufactured by Japan Epoxy Resin, Epototo YDF-170, YDF-175, YDF-2004 manufactured by Toto Kasei Co., Ltd. (all trade names) Type epoxy resin; Epototo ST-2004, ST-200 manufactured by Toto Kasei Co., Ltd. , ST-3000 (both trade names) and other hydrogenated bisphenol A type epoxy resins; Japan Epoxy Resin Co., Ltd. JER604, Toto Kasei Co., Ltd. Epototo YH-434, Sumitomo Chemical Co., Ltd. Glycidylamine type epoxy resin such as Sumi-Epoxy ELM-120 (all trade names); Cycloside 2021 (trade name) manufactured by Daicel Chemical Industries, Ltd .; Japan Epoxy Resin Co., Ltd. Trihydroxyphenylmethane type epoxy resins such as YL-933, Nippon Kayaku Co., Ltd. EPPN-501, EPPN-502 (all trade names); YL-6056, YX-4000 made by Japan Epoxy Resin Co., Ltd. , Bixylenol type or biphenol type epoxy resins such as YL-6121 (both trade names) or their Compound: Bisphenol S such as EBPS-200 manufactured by Nippon Kayaku Co., Ltd., EPX-30 manufactured by Asahi Denka Kogyo Co., Ltd., EXA-1514 manufactured by Dainippon Ink & Chemicals, Inc. (all trade names) Type epoxy resin; bisphenol A novolak type epoxy resin such as JER157S (trade name) manufactured by Japan Epoxy Resin Co., Ltd .; tetraphenylolethane type epoxy resin such as JERYL-931 (trade name) manufactured by Japan Epoxy Resin Co., Ltd. A heterocyclic epoxy resin such as TEPIC (trade name) manufactured by Nissan Chemical Co., Ltd .; a diglycidyl phthalate resin such as Blemmer DGT (trade name) manufactured by Nippon Oil &Fats; ZX- manufactured by Toto Kasei Co., Ltd. Tetraglycidylxylenoylethane resin such as 1063 (trade name); ESN-190, ESN-360, manufactured by Nippon Steel Chemical Co., Ltd. Naphthalene group-containing epoxy resins such as HP-4032, EXA-4750, EXA-4700 (all trade names) manufactured by NKI Chemical Industry Co., Ltd .; HP-7200, HP-7200H manufactured by Dainippon Ink & Chemicals, Inc. Epoxy resins having a dicyclopentadiene skeleton such as (all trade names); Glycidyl methacrylate copolymer epoxy resins such as CP-50S and CP-50M (all trade names) manufactured by NOF Corporation; and hydantoin Type epoxy resin, copolymerized epoxy resin of cyclohexylmaleimide and glycidyl methacrylate, secondary alcoholic hydroxyl group obtained by reacting 1,5-dihydroxynaphthalene and bisphenol A type epoxy resin with epihalohydrin Polyfunctional epoxy resin (International Publication WO 01/02 774 JP) and the like, can be used alone or in combination of two or more. For an electronic material, a polyfunctional epoxy resin having 3 or more epoxy groups in one molecule is preferable, and among these, a novolak type epoxy resin is particularly preferable from the viewpoint of physical properties of a cured product.

  As aldehydes, aliphatic saturated aldehydes such as acetaldehyde, propionaldehyde, butyraldehyde, valeraldehyde, piperaldehyde, capronaldehyde, caprylaldehyde, tridecylaldehyde, myristic aldehyde, pentadecylaldehyde, palmitic aldehyde, stearaldehyde; acrolein, Aliphatic unsaturated aldehydes such as crotonaldehyde, propiolaldehyde, benzaldehyde, 0-, m-, or p-tolualdehyde, salicylaldehyde, cinnamaldehyde, aromatic aldehydes such as α- or β-naphthaldehyde; A heterocyclic aldehyde etc. are mentioned, It can use individually or in combination of 2 or more types.

  Examples of the acid used as a catalyst for the reaction include phosphoric acid, hydrochloric acid, sulfuric acid, phosphotungstic acid, boron trifluoride ether complex, silicotungstic acid, trifluoromethanesulfonic acid, and polyphosphoric acid. Among these, electrons From the viewpoint of materials, phosphoric acid is preferable. The amount of the acid used is preferably 0.001% by mass or more and 20% by mass or less with respect to the polyfunctional epoxy resin, more preferably 0.01 to 5% by mass, particularly preferably 0.01 to 3%. % By mass. If the ratio of the acid exceeds 20% by mass, gelation may occur. On the other hand, if it is less than 0.001% by mass, the reactivity between the polyfunctional epoxy resin and the aldehyde decreases, which is not preferable.

  The reaction between the polyfunctional epoxy resin and the aldehyde is preferably carried out in a carbonyl group-containing solvent such as an aldehyde or a ketone, particularly in terms of yield, in a mixed solvent of aldehyde or aldehyde and ketone. And other solvents such as a mixed solvent of aldehyde and toluene, or a mixed solvent of aldehyde and carbitol can also be used. 0-100 degreeC of reaction temperature is preferable, More preferably, it is 10-80 degreeC. If the reaction temperature exceeds 100 ° C., gelation may occur, which is not preferable. On the other hand, when the reaction temperature is less than 0 ° C., the reactivity is lowered, which is not preferable.

  The compounding ratio in the composition of the epoxy resin (A) having a 1,3-dioxolane ring obtained in this way is a carboxyl group-containing compound (B) and / or a carboxyl group-containing photosensitive compound (B ′) described later. A ratio of 5 to 100 parts by mass is appropriate with respect to 100 parts by mass (total amount or single amount in the case of single use; the same applies hereinafter as solid content).

  Next, the carboxyl group-containing compound (B) and the carboxyl group-containing photosensitive compound (B ′) are compounds having at least one, preferably two or more carboxyl groups in one molecule (this specification) In some cases, these are collectively referred to as a carboxyl group-containing compound). Specifically, both a carboxyl group-containing compound (B) that does not itself have an ethylenically unsaturated double bond and a carboxyl group-containing photosensitive compound (B ′) that has an ethylenically unsaturated double bond are used. Although it is possible and it is not limited to a specific thing, the compound (any of an oligomer and a polymer) as listed below can be used conveniently especially.

(1) a carboxyl group-containing compound obtained by copolymerizing an unsaturated carboxylic acid (a) and a compound (b) having an unsaturated double bond,
(2) a carboxyl group-containing photosensitive compound obtained by adding an ethylenically unsaturated group as a pendant to a copolymer of unsaturated carboxylic acid (a) and 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 compound obtained by reacting a saturated or unsaturated polybasic acid anhydride (d) with the 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 compound 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 compound obtained by preferably esterifying, and further reacting the generated hydroxyl group with a saturated or unsaturated polybasic acid anhydride (d),
(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 compound 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 compound 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 compound obtained by reacting a hydroxyl group-containing polymer (j) with a saturated or unsaturated polybasic acid anhydride (d). A carboxyl group-containing photosensitive compound 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). Compound,
(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). Compound,
(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 compound or A carboxyl group-containing photosensitive compound 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 photosensitive compound,
(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 photosensitive compound, and (14) a reaction product of a novolak-type phenol resin (s) with an alkylene oxide (t) and / or a cyclic carbonate (u) with an unsaturated monocarboxylic acid (h), A carboxyl group-containing photosensitive compound obtained by reacting the obtained reaction product with a saturated or unsaturated polybasic acid anhydride (d).

  The carboxyl group-containing compound (1) includes an unsaturated carboxylic acid (a) such as (meth) acrylic 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 compound (2) is a copolymer of an unsaturated carboxylic acid (a) and a compound (b) having an unsaturated double bond. A compound having an ethylenically unsaturated group such as a vinyl group, an allyl group or a (meth) acryloyl group and a reactive group such as an epoxy group or an acid chloride such as glycidyl (meth) acrylate is reacted with a part of the carboxyl group of A compound in which an unsaturated double bond of the compound is 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 compound is soluble in an alkaline aqueous solution. It is.

  The carboxyl group-containing photosensitive compound (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 epoxy group of the copolymer of the compound (b) having an unsaturated double bond is reacted with the carboxyl group of the unsaturated carboxylic acid (a), and the unsaturated double bond of the unsaturated carboxylic acid is used as a side chain. At the same time, the secondary hydroxyl group produced by the above addition reaction is esterified with polybasic acid anhydride (d) such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, etc. It is a compound into which a group is introduced.

  The carboxyl group-containing photosensitive compound (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, for example, a hydroxyalkyl (meth) acrylate, a monomer obtained by reacting caprolactone with (meth) acrylate, It is a compound in which a hydroxyl group such as a macromonomer obtained by reacting a (meth) acrylate with a polycaprolactone oligomer is reacted to form a half ester, and an unsaturated double bond of the compound (f) is introduced into a side chain.

  The carboxyl group-containing photosensitive compound (5) is a bisphenol A type, bisphenol F type, bisphenol S type, phenol novolac type, cresol novolac type, biphenol type, bixylenol type, N-glycidyl type or the like. The epoxy group of the functional epoxy compound (g) is reacted with a carboxyl group of an unsaturated monocarboxylic acid (h) such as (meth) acrylic acid to produce, for example, an epoxy acrylate and a secondary product produced by the above addition reaction. It is a compound in which the polybasic acid anhydride (d) is esterified to a hydroxyl group and a carboxyl group is introduced into the side chain.

  The carboxyl group-containing compound (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 compound obtained by reacting an acid, an aromatic group-containing alkyl carboxylic acid or the like, and adding the polybasic acid anhydride (d) to the generated secondary hydroxyl group.

The carboxyl group-containing compound (7) has a hydroxyl group-containing polymer (j), such as an olefinic hydroxyl group-containing polymer, an acrylic polyol, a rubber polyol, a polyvinyl acetal, a styrene allyl alcohol resin, and celluloses. It is a compound in which a carboxyl group is introduced by reacting the relatively weak polybasic acid anhydride (d).
On the other hand, in the carboxyl group-containing photosensitive compound (8), the carboxyl group of the carboxyl group-containing compound (7) is reacted with the epoxy group of the compound (c) having an unsaturated double bond with the epoxy group, It is a compound in which an unsaturated double bond of the compound (c) is introduced into the side chain.

In the synthesis reaction of the carboxyl group-containing photosensitive compound (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 compound of (10), the reaction product (I) is reacted with the polybasic acid anhydride (d), and then the unsaturated group-containing polyhydric acid produced is produced. The unsaturated group-containing monoisocyanate (m) is preferably reacted with the hydroxyl group in the carboxylic acid compound.
Specific examples of the unsaturated group-containing monoisocyanate (m) include, for example, methacryloyl isocyanate, methacryloyloxyethyl isocyanate, organic diisocyanates (for example, tolylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, etc.) and the above-mentioned 1 Examples thereof include reaction products obtained by reacting (meth) acrylates having one hydroxyl group in the molecule at an equimolar ratio.

  The carboxyl group-containing photosensitive compound 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 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 compound with the polybasic acid anhydride (d), the binding site is thermally formed. It is a compound that is difficult to be cut and has excellent thermal stability.

  The carboxyl group-containing photosensitive compounds (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. Bisepoxy resins (p) such as biphenol type epoxy resins and bixylenol type epoxy resins, and dicarboxylic acids (q) such as oxalic acid, malonic acid, succinic acid, phthalic acid and isophthalic acid, or bisphenol A, bisphenol F, etc. An unsaturated double bond is introduced into the reaction product with the bisphenol (r), and then a polybasic acid anhydride (d) is further added to the secondary hydroxyl group produced by the above reaction or the remaining hydroxyl group. By making it react, it is set as resin excellent in thermal stability. The introduction of unsaturated double bonds generally involves reacting the ethylenically unsaturated groups such as vinyl group, allyl group, (meth) acryloyl group, etc. with the remaining hydroxyl groups, carboxyl groups, etc. and the generated hydroxyl groups. 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 compound (14) is excellent in flexibility and elongation due to chain extension by addition reaction of alkylene oxide (t) and / or cyclic carbonate (u) of novolak type phenol resin (s), and Unsaturated monocarboxylic acid (h) and polybasic acid anhydride (d) are added to the terminal hydroxyl group produced by the addition reaction of alkylene oxide, and the unsaturated group or carboxyl group is present on the same side chain. In addition, since each is located at the end of the side chain, it has excellent reactivity, and has excellent alkali developability due to the presence of a terminal carboxyl group away from the main chain. Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, trimethylene oxide, tetrahydrofuran, and tetrahydropyran. Examples of the cyclic carbonate (u) include ethylene carbonate, propylene carbonate, butylene carbonate, and 2,3-carbonate propyl methacrylate. Preferably, 5-membered ring ethylene carbonate and propylene carbonate are reactive and have a supply system. To preferred. These carbonate compounds can be used alone or in admixture of two or more.

The acid value of the carboxyl group-containing compound (B) and the carboxyl group-containing photosensitive compound (B ′) as described above is preferably 20 to 200 mgKOH / g, more preferably 50 to 120 mgKOH / g. When the acid value is lower than 20 mgKOH / g, the solubility in an alkaline aqueous solution is deteriorated, and development of the formed coating film becomes difficult. On the other hand, if it is higher than 200 mgKOH / g, the surface of the exposed area is developed regardless of the exposure conditions, which is not preferable.
The carboxyl group-containing compound (B) and the carboxyl group-containing photosensitive compound (B ′) as described above can be used alone or in combination of two or more.

  When only the carboxyl group-containing compound (B) is used, the compound itself has no ethylenically unsaturated double bond. ) It is necessary to use an acrylate compound (C).

  Examples of the photosensitive (meth) acrylate compound (C) include hydroxyl group-containing acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, pentaerythritol triacrylate, and dipentaerythritol pentaacrylate. Water-soluble acrylates such as polyethylene glycol diacrylate and polypropylene glycol diacrylate; polyfunctional polyester acrylates of polyhydric alcohols such as trimethylolpropane tri (meth) acrylate, pentaerythritol tetraacrylate and dipentaerythritol hexaacrylate; Multifunctional alcohols such as trimethylolpropane and hydrogenated bisphenol A or polyhydric phenols such as bisphenol A and biphenol Acrylates of ethylene oxide adduct and / or propylene oxide adduct; polyfunctional or monofunctional polyurethane acrylate which is an isocyanate modification of the above hydroxyl group-containing acrylate; bisphenol A diglycidyl ether, hydrogenated bisphenol A diglycidyl ether or phenol Epoxy acrylates that are (meth) acrylic acid adducts of novolac epoxy resins; caprolactone-modified ditrimethylolpropane tetraacrylate, ε-caprolaclone-modified dipentaerythritol acrylate, caprolactone-modified hydroxypivalic acid neopentyl glycol ester diacrylate, etc. Acrylates and methacrylates corresponding to the above acrylates. Can be used alone or in combination of two or more. Among these, a polyfunctional (meth) acrylate compound having two or more (meth) acryloyl groups in one molecule is preferable. The purpose of using these photosensitive (meth) acrylate compounds is to have photocurability in the composition. Photosensitive (meth) acrylate compounds that are liquid at room temperature are used for the purpose of imparting photocurability to the composition, as well as for adjusting the composition to a viscosity suitable for various coating methods, and for assisting solubility in alkaline aqueous solutions. Also fulfills. However, if a large amount of liquid photosensitive (meth) acrylate compound is used at room temperature, the dryness of the coating film cannot be obtained, and the characteristics of the coating film tend to deteriorate. It is not preferable. The blending amount of the photosensitive (meth) acrylate compound (C) is preferably 100 parts by mass or less with respect to 100 parts by mass of the carboxyl group-containing compound (B). In addition, a photosensitive (meth) acrylate compound (C) can be blended with the carboxyl group-containing photosensitive compound (B ′) for the purpose of increasing photoreactivity. In this case, the compounding amount of the photosensitive (meth) acrylate compound (C) is preferably 100 parts by mass or less with respect to 100 parts by mass of the carboxyl group-containing photosensitive compound (B ′). In this specification, “(meth) acrylate” is a term that collectively refers to acrylate and methacrylate, and the same applies to other similar expressions.

  Examples of the photopolymerization initiator (D) include benzoin and benzoin alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2, Acetophenones such as 2-diethoxy-2-phenylacetophenone and 1,1-dichloroacetophenone; 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2- Aminoacetophenones such as dimethylamino-1- (4-morpholinophenyl) -butan-1-one, N, N-dimethylaminoacetophenone; 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1- Chloro Anthraquinones such as nthraquinone; thioxanthones such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone and 2,4-diisopropylthioxanthone; ketals such as acetophenone dimethyl ketal and benzyldimethyl ketal; benzoylper Organic peroxides such as oxide and cumene peroxide; 2,4,5-triarylimidazole dimer; Riboflavin tetrabutyrate; Thiols such as 2-mercaptobenzimidazole, 2-mercaptobenzoxazole and 2-mercaptobenzothiazole Compound; Organic halogen compounds such as 2,4,6-tris-s-triazine, 2,2,2-tribromoethanol, tribromomethylphenylsulfone; benzophenone, 4,4'-bisdie Benzophenones or xanthones such as Le aminobenzophenone; and 2,4,6-trimethylbenzoyl diphenylphosphine oxide. These known and commonly used photopolymerization initiators can be used alone or as a mixture of two or more thereof. Further, N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, pentyl-4- Photoinitiator aids such as tertiary amines such as dimethylaminobenzoate, triethylamine, triethanolamine can be added. A titanocene compound such as CGI-784 (manufactured by Ciba Specialty Chemicals Co., Ltd.) having absorption in the visible light region can also be added to promote the photoreaction. Particularly preferred photopolymerization initiators are 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2- Dimethylamino-1- (4-morpholinophenyl) -butan-1-one and the like, but is not particularly limited thereto, and absorbs light in the ultraviolet light or visible light region, such as (meth) acryloyl group As long as the unsaturated group is radically polymerized, it is not limited to a photopolymerization initiator and a photoinitiator aid, and can be used alone or in combination. And the usage-amount is 0.5-0.5 with respect to the said carboxyl group containing compound (B) and / or a carboxyl group-containing photosensitive compound (B ') 100 mass parts (total amount or single amount in the case of single use). A proportion of 25 parts by weight is preferred.

Further, the curable composition of the present invention includes the epoxy resin (A) having the 1,3-dioxolane ring, the carboxyl group-containing compound (B), the carboxyl group-containing photosensitive compound (B ′), and the photosensitive (meth). In order to dissolve the acrylate compound (C) and adjust the composition to a viscosity suitable for the coating method, an organic solvent can be blended.
Examples of the organic solvent include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether , Glycol ethers such as diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether; ethyl acetate, butyl acetate, ethylene glycol monoethyl ether acetate , Ethylene glycol monobutyl ether Acetates such as cetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate; alcohols such as ethanol, propanol, ethylene glycol, propylene glycol; octane, decane, etc. Aliphatic hydrocarbons; petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha. These organic solvents can be used alone or as a mixture of two or more. The compounding quantity of the organic solvent can be made into arbitrary quantity according to a use etc.

  Moreover, the curable composition of this invention can mix | blend a curing catalyst to such an extent that the storage stability is not impaired. Examples of the curing catalyst include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- ( Imidazole derivatives such as 2-cyanoethyl) -2-ethyl-4-methylimidazole; dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine Amine compounds such as 4-methyl-N, N-dimethylbenzylamine; hydrazine compounds such as adipic acid hydrazide and sebacic acid hydrazide; and phosphorus compounds such as triphenylphosphine. Examples of commercially available products include 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (both trade names of imidazole compounds) manufactured by Shikoku Kasei Co., Ltd., U-CAT3503N manufactured by San Apro Co., Ltd. U-CAT3502T (all are trade names of blocked isocyanate compounds of dimethylamine), DBU, DBN, U-CATSA102, U-CAT5002 (all are bicyclic amidine compounds and salts thereof), and the like. In particular, as long as it is for improving thermosetting properties, it is not limited to these, as long as it is a curing catalyst for a compound having a cyclic ether, or a compound that promotes the reaction between a compound having a cyclic ether and a carboxylic acid, You may use individually or in mixture of 2 or more types. Guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-4,6-diamino-S-triazine, 2 S-triazine derivatives such as -vinyl-4,6-diamino-S-triazine / isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine / isocyanuric acid adduct can also be used, These compounds are preferably used in combination with the curing catalyst. The amount of the curing catalyst is sufficient in the usual quantitative ratio, for example, 100 parts by mass of the carboxyl group-containing compound (B) and / or carboxyl group-containing photosensitive compound (B ′) (total amount or when used alone) Is a ratio of 0.1 to 20 parts by mass, preferably 0.5 to 15.0 parts by mass with respect to a single amount.

  Furthermore, the curable composition of this invention can mix | blend the compound which has cyclic ether as a thermosetting component to such an extent that the storage stability is not reduced. Examples of the compound having two or more cyclic ethers in one molecule include oxirane compounds, oxetane compounds, and oxolane compounds.

  As the oxirane compound, for example, a polyfunctional epoxy resin exemplified in the synthesis of the epoxy resin (A) having a 1,3-dioxolane ring can be used.

Examples of the oxetane compound include 3,7-bis (3-oxetanyl) -5-oxa-nonane, 3,3 ′-(1,3- (2-methylenyl) propanediylbis (oxymethylene)) bis- ( 3-ethyloxetane), 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, 1,2-bis [(3-ethyl-3-oxetanylmethoxy) methyl] ethane, 1,3- Bis [(3-ethyl-3-oxetanylmethoxy) methyl] propane, ethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenylbis (3-ethyl-3-oxetanylmethyl) ether, triethylene glycol Bis (3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycol bis (3-ethyl- -Oxetanylmethyl) ether, tricyclodecanediyldimethylene (3-ethyl-3-oxetanylmethyl) ether, trimethylolpropane tris (3-ethyl-3-oxetanylmethyl) ether, 1,4-bis (3-ethyl- 3-oxetanylmethoxy) butane, 1,6-bis (3-ethyl-3-oxetanylmethoxy) hexane, pentaerythritol tris (3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis (3-ethyl-3-oxetanyl) Methyl) ether and the like.
The compounds having a cyclic ether as described above can be used alone or in combination of two or more.

  The curable composition of the present invention further contains, as necessary, barium sulfate, barium titanate, amorphous silica, crystalline silica, fused silica, spherical silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, Known or commonly used inorganic fillers such as aluminum hydroxide and mica can be used alone or in combination of two or more. These are used for the purpose of suppressing curing shrinkage of the coating film and improving properties such as adhesion and hardness. The compounding amount of the inorganic filler is 10 to 100 parts by mass (total amount or single amount in the case of single use) of the carboxyl group-containing compound (B) and / or the carboxyl group-containing photosensitive compound (B ′). A proportion of 300 parts by mass, preferably 30 to 200 parts by mass is appropriate.

  Further, the curable composition of the present invention may further include a known and commonly used colorant such as phthalocyanine blue, phthalocyanine green, iodin green, disazo yellow, crystal violet, titanium oxide, carbon black, naphthalene black, if necessary. Known and commonly used thermal polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, t-butylcatechol, pyrogallol and phenothiazine, known and commonly used thickeners such as fine silica, organic bentonite and montmorillonite, silicones, fluorines, polymers, etc. Known and conventional additives such as a defoaming agent and / or a leveling agent, an imidazole series, a thiazole series, a triazole series silane coupling agent, and the like can be blended.

  Furthermore, the curable composition of this invention can mix | blend flame retardants, such as a halogenated flame retardant, a phosphorus flame retardant, and an antimony flame retardant, for the purpose of obtaining a flame retardance. The compounding amount of the flame retardant is usually 1 with respect to 100 parts by mass (total amount or single amount when used alone) of the carboxyl group-containing compound (B) and / or carboxyl group-containing photosensitive compound (B ′). -200 mass parts, Preferably it is 5-50 mass parts. When the blending amount of the flame retardant is in the above range, the flame retardancy, solder heat resistance, and electrical insulation of the composition are highly balanced and suitable.

  Moreover, water can also be added to the curable composition of this invention for the fall of flammability. When water is added, the carboxyl group of the carboxyl group-containing compound (B) and / or the carboxyl group-containing photosensitive compound (B ′) is converted to an amine such as trimethylamine or triethylamine, N, N-dimethylaminoethyl ( By making a salt with a (meth) acrylate resin having a tertiary amino group such as (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylamide, acryloylmorpholine, etc., the curable composition of the present invention is adapted to water. It is preferable to make it.

  The curable composition of this invention can also be made into the form of the dry film provided with the support body and the layer which consists of the said curable composition formed on this support body. Preferably, a peelable cover film is further laminated on the curable composition layer of the film.

  A plastic film is used as the support, and a plastic film such as a polyester film such as polyethylene terephthalate, a polyimide film, a polyamideimide film, a polypropylene film, or a polystyrene film is preferably used. Here, about the thickness of a support body, it selects suitably in the range of 10-150 micrometers.

  The curable composition layer on the support is coated with a uniform thickness on the support with a comma coater, blade coater, lip coater, rod coater, squeeze coater, reverse coater, transfer roll coater or the like. It is obtained by volatilizing the solvent by heating and drying, but the thickness is not particularly limited and is appropriately selected within the range of 10 to 150 μm.

  As the cover film, a polyethylene film, a polypropylene film, a Teflon (registered trademark) film, a surface-treated paper or the like is generally used. The cover film is not particularly limited as long as the adhesive force between the curable composition layer and the cover film is smaller than the adhesive force between the curable composition layer and the support.

  The curable composition of the present invention having the above composition is diluted as necessary to adjust the viscosity to be suitable for the coating method. For example, this is applied to a printed wiring board formed with a circuit by a screen printing method or a curtain. A tack-free coating film can be formed by applying the coating method, spray coating method, roll coating method or the like and evaporating and drying an organic solvent contained in the composition at a temperature of about 60 to 100 ° C., for example. Moreover, in the case of the form of the dry film provided with the support body and the layer which consists of the said curable composition formed on this support body, it bonds together using a hot roll laminator etc. to the printed wiring board by which the circuit was formed ( By bonding the curable composition layer and the printed wiring board on which the circuit is formed, the coating film can be formed on the printed wiring board on which the circuit is formed. In the case of a dry film provided with a peelable cover film on the curable composition layer of the film, after the cover film is peeled off, the curable composition layer and the printed wiring board on which the circuit is formed come into contact. Thus, it is possible to form a coating film on a printed wiring board on which a circuit is formed by laminating using a hot roll laminator or the like.

  After forming a coating film on a printed wiring board on which a circuit is formed (if the dry film is used, the support is not peeled off), and then directly irradiating active energy rays such as laser light as a pattern or pattern The resist pattern can be formed by selectively exposing with an active energy ray through a photomask on which the film is formed, and developing the unexposed portion with a dilute alkaline aqueous solution (if the dry film is used, the support is peeled off and developed To do). Thereafter, only by heat curing, or by heat curing after irradiation of active energy rays or final curing (main curing) by irradiation of active energy rays after heat curing, electrical insulation, PCT resistance, adhesion, solder heat resistance, A cured film (cured product) excellent in chemical resistance, electroless gold plating resistance and the like is formed.

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

  EXAMPLES Hereinafter, although an Example etc. are shown and this invention is demonstrated more concretely, this invention is not limited to these Examples. In the following description, “part” means part by mass unless otherwise specified.

Synthesis example 1
In a reaction vessel equipped with a stirrer, a thermometer, and a dropping funnel for continuous dripping, 200 parts of a novolak type epoxy resin (Epototo YDCN-704 manufactured by Tohto Kasei Co., Ltd., epoxy equivalent 200 g / eq.) And propionaldehyde 100 Parts were charged and stirred at 20 to 25 ° C. to dissolve the epoxy resin in propionaldehyde. Next, a mixed solution of 2 parts of 85% phosphoric acid and 40 parts of propionaldehyde was gradually added dropwise and reacted at 20 to 25 ° C. for 20 hours. Thereafter, the liquid temperature was raised to 35 to 40 ° C., and the mixture was reacted for 4 hours. A reaction solution was obtained. The reaction ratio of propionaldehyde to the starting epoxy resin was about 0.15 equivalent of carbonyl group per equivalent of epoxy group.

Synthesis example 2
In a reaction vessel equipped with a stirrer, a thermometer, and a dropping funnel for continuous dripping, 200 parts of a novolak type epoxy resin (Epototo YDCN-704 manufactured by Tohto Kasei Co., Ltd., epoxy equivalent 200 g / eq.) And propionaldehyde 10 And 90 parts of dipropylene glycol monomethyl ether were added and stirred at 20 to 25 ° C. to dissolve the epoxy resin. Next, a mixed solution of 2 parts of 85% phosphoric acid and 40 parts of propionaldehyde was gradually added dropwise and reacted at 20 to 25 ° C. for 20 hours. Thereafter, the liquid temperature was raised to 35 to 40 ° C. and reacted for 4 hours. The nonvolatile content was 62%, the solid content epoxy equivalent was 240 g / eq. A reaction solution was obtained. The reaction ratio of propionaldehyde to the starting epoxy resin was about 0.13 equivalent of carbonyl group per equivalent of epoxy group.

Synthesis example 3
To an autoclave equipped with a thermometer, a nitrogen introduction device / alkylene oxide introduction device and a stirring device, a novolac type cresol resin (trade name “Shonol CRG951” manufactured by Showa Polymer Co., Ltd., phenolic hydroxyl group equivalent: 119.4 g / eq) .) 119.4 parts, 1.19 parts of potassium hydroxide, and 119.4 parts of toluene were charged, and the system was purged with nitrogen while stirring and heated. Next, 63.8 parts 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 parts 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 alcoholic hydroxyl group equivalent was 182.2 g / eq. A novolak-type cresol resin propylene oxide reaction solution was obtained. This was an average of about 1.08 mole of alkylene oxide added per equivalent of phenolic hydroxyl group.
293.0 parts of a propylene oxide reaction solution of the obtained novolac-type cresol resin, 43.2 parts of acrylic acid, 11.53 parts of methanesulfonic acid, 0.18 part of methylhydroquinone, and 252.9 parts of toluene were mixed with a stirrer and a temperature. A reactor equipped with a total and an air blowing tube was charged, air was blown at a rate of 10 ml / min, and the reaction was carried out at 110 ° C. for 12 hours while stirring. 12.6 parts of water was distilled from the water produced by the reaction as an azeotrope with toluene. Thereafter, the reaction solution was cooled to room temperature, neutralized with 35.35 parts of a 15% aqueous sodium hydroxide solution, and then washed with water. Thereafter, toluene was distilled off while substituting 118.1 parts of diethylene glycol monoethyl ether acetate with an evaporator to obtain a novolak acrylate resin solution.
Next, 332.5 parts of the obtained novolak acrylate resin solution and 1.22 parts of triphenylphosphine were charged into a reactor equipped with a stirrer, a thermometer, and an air blowing tube, and air was supplied at a rate of 10 ml / min. While blowing and stirring, 60.8 parts of tetrahydrophthalic anhydride was gradually added, reacted at 95 to 101 ° C. for 6 hours, cooled and taken out. The carboxyl group-containing photosensitive compound thus obtained had a nonvolatile content of 70.6% and a solid content acid value of 87.7 mgKOH / g.

Synthesis example 4
In a reaction vessel equipped with a gas introduction tube, a stirring device, a cooling tube, a thermometer, and a dropping funnel for continuous dropping of an alkali metal hydroxide aqueous solution, a phenolic hydroxyl group equivalent of 80 g / eq. 1,5-dihydroxynaphthalene of 224 parts and 1075 parts of bisphenol A type epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd., JER828, epoxy equivalent of 189 g / eq.) Were dissolved at 110 ° C. with stirring in a nitrogen atmosphere. I let you. Thereafter, 0.65 part of triphenylphosphine was added, the temperature in the reaction vessel was raised to 150 ° C., and the mixture was allowed to react for about 90 minutes while maintaining the temperature at 150 ° C., whereby an epoxy equivalent of 452 g / equivalent epoxy compound ( a) was obtained. Next, the temperature in the flask was cooled to 40 ° C., 1920 parts of epichlorohydrin, 1690 parts of toluene, and 70 parts of tetramethylammonium bromide were added, and the temperature was raised to 45 ° C. and maintained with stirring. Thereafter, 364 parts of a 48 wt% aqueous sodium hydroxide solution were continuously added dropwise over 60 minutes, and then reacted for another 6 hours. After completion of the reaction, excess epichlorohydrin and most of toluene were recovered by distillation under reduced pressure, and the reaction product containing by-product salt and toluene was dissolved in methyl isobutyl ketone and washed with water. After the organic solvent layer and the aqueous layer were separated, methyl isobutyl ketone was distilled off from the organic solvent layer under reduced pressure to obtain an epoxy equivalent of 277 g / eq. The polynuclear epoxy resin (b) was obtained. When the obtained polynuclear epoxy resin (b) is calculated from the epoxy equivalent, about 1.59 of 1.98 alcoholic hydroxyl groups in the epoxy compound (a) are epoxidized. Therefore, the epoxidation rate of the alcoholic hydroxyl group is about 80%.
Next, 277 parts of the polynuclear epoxy resin (b) is placed in a flask equipped with a stirrer, a cooling tube and a thermometer, 290 parts of carbitol acetate is added, and heated to dissolve, 0.46 parts of methylhydroquinone and triphenylphosphine 1.38 parts were added and heated to 95-105 ° 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., and 129 parts of tetrahydrophthalic anhydride was added and reacted for 8 hours. In the reaction, oxidation of the reaction solution by potentiometric titration and total oxidation measurement are performed, followed by the obtained addition rate, and the end point is 95% or more of the reaction rate. The carboxyl group-containing photosensitive resin thus obtained had a nonvolatile content of 62% and a solid content acid value of 100 mgKOH / g.

Synthesis example 5
A cresol novolak type epoxy resin Epicron N-695 (Dainippon Ink Chemical Co., Ltd., epoxy equivalent: 220) 220 parts was placed in a four-necked flask equipped with a stirrer and reflux condenser, and diethylene glycol monoethyl ether acetate. 220 parts were added and dissolved by heating. Next, 0.46 part of hydroquinone as a polymerization inhibitor and 1.38 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 and reacted for 8 hours. After cooling, the reaction product was taken out. The carboxyl group-containing photosensitive compound thus obtained had a nonvolatile content of 64% and a solid content acid value of 97 mgKOH / g.

Examples 1-7 and Comparative Examples 1-3
Using the epoxy resin reactant solution obtained in Synthesis Examples 1 and 2 and the carboxyl group-containing photosensitive compound solution obtained in Synthesis Examples 3 to 5, the composition shown in Table 1 (numerical values are parts by mass) Each component was blended according to the above, kneaded separately with a three-roll mill, each curable composition was prepared, and the storage stability was evaluated. Next, this is applied to the surface-treated copper through-hole printed wiring board that has been patterned so as to have a thickness of 20 to 30 μm using a 100 mesh polyester screen by a screen printing method. Is dried for 30 minutes using a hot air drier at 80 ° C., and then a negative film having a resist pattern is closely adhered to the coating film, and an ultraviolet exposure device (manufactured by Oak Manufacturing Co., Ltd., model HMW-680GW) is used. After irradiation with ultraviolet rays (exposure 600 mJ / cm ² ), develop with 1 wt% aqueous sodium carbonate solution for 60 seconds at a spray pressure of 2.0 kg / cm ² , and then heat cure for 60 minutes with a hot air dryer at 150 ° C. A test substrate was prepared.
For each test substrate having the cured film obtained, each test of crack resistance, PCT resistance, adhesion, solder heat resistance, acid resistance, alkali resistance, and electroless gold plating resistance by the test methods and evaluation methods described below. Was done.
In addition, using a B pattern of a printed circuit board (thickness 1.6 mm) defined by IPC instead of a copper through-hole printed wiring board, a test board was produced under the same conditions as described above, and an electrical insulation resistance test was performed. .

(1) Storage stability:
The compositions in Table 1 were placed in a 40 ° C. heat insulation bath and evaluated according to the following criteria.
○: not gelled Δ: slightly gelled ×: gelled Test results are shown in Table 2.

(2) Crack resistance:
The crack resistance of the cured film was evaluated according to the following criteria using Thermal Shock Chamber NT 1020W manufactured by Enomoto Kasei Co., Ltd. with -65 to 150 ° C as one cycle. However, only the sample which did not gel was tested.
○: Cracks occurred at 300 cycles or more. Δ: Cracks occurred at 200 to 299 cycles. X: Cracks occurred at 199 cycles or less.

(3) PCT resistance:
The PCT resistance of the cured film was evaluated according to the following criteria under the conditions of 121 ° C. and 50 hours in saturated steam. However, only the sample which did not gel was tested.
○: The cured film has no blistering, peeling, or discoloration Δ: The cured film has slight blistering, peeling, or discoloration ×: The cured film has blistering, peeling, or discoloration Table 4 shows the test results.

(4) Adhesion:
According to the test method of JIS D 0202, the cured film was cross-cut in a grid pattern, and then the peelability after the peeling test with a cellophane adhesive tape was visually determined. However, only the sample which did not gel was tested.
○: 100/100 with no peeling Δ: 50/100 to 90/100
X: 0/100 to 50/100
The test results are shown in Table 5.

(5) Solder heat resistance:
According to the test method of JIS C 6481, the test substrate was immersed in a 260 ° C. solder bath three times for 10 seconds, and the change in appearance was evaluated. In addition, as a post flux (rosin type), a flux according to JIS C 6481 was used. However, only the sample which did not gel was tested.
○: No change in appearance △: Discoloration of the cured film is observed ×: The cured film is floated, peeled off, and solder is submerged. Table 6 shows the test results.

(6) Acid resistance:
The test substrate was taken out after being immersed in a 10 vol% sulfuric acid aqueous solution at 20 ° C. for 30 minutes, and the state of the cured film was evaluated according to the following criteria. However, only the sample which did not gel was tested.
○: No change is observed Δ: Only a slight change ×: The cured film has blisters or swelling drops Test results are shown in Table 7.

(7) Alkali resistance:
The test substrate was evaluated in the same manner as in the acid resistance test except that the 10 vol% sulfuric acid aqueous solution was replaced with a 10 wt% sodium hydroxide aqueous solution. However, only the sample which did not gel was tested.
The test results are shown in Table 8.

(8) Electroless gold plating resistance:
The test substrate was subjected to electroless gold plating according to the steps described below, and the test substrate was subjected to a change in appearance and a peeling test using a cellophane adhesive tape, and the peeled state of the cured film was determined according to the following criteria. However, only the sample which did not gel was tested.
○: No change in appearance and no peeling of the cured film.
(Triangle | delta): Although there is no change of an external appearance, there exists slight peeling in a cured film.
X: Lifting of the cured film is observed, plating lag is observed, and peeling of the cured film is large in the peeling test.
The test results are shown in Table 9.

Electroless gold plating process:
1. Degreasing: The test substrate was dipped in an acidic degreasing solution at 30 ° C. (manufactured by Nippon McDermid Co., Ltd., 20 vol% aqueous solution of Metex L-5B) for 3 minutes.
2. Rinsing: The test substrate was immersed in running water for 3 minutes.
3. Soft etch: The test substrate was immersed in a 14.3 wt% ammonium persulfate aqueous solution at room temperature for 3 minutes.
4). Rinsing: The test substrate was immersed in running water for 3 minutes.
5). Acid immersion: The test substrate was immersed in a 10 vol% sulfuric acid aqueous solution at room temperature for 1 minute.
6). Washing with water: The test substrate was immersed in running water for 30 seconds to 1 minute.
7). Catalyst application: The test substrate was immersed for 7 minutes in a 30 ° C. catalyst solution (manufactured by Meltex, 10 vol% aqueous solution of metal plate activator 350).
8). Rinsing: The test substrate was immersed in running water for 3 minutes.
9. Electroless nickel plating: The test substrate was immersed in a nickel plating solution (manufactured by Meltex Co., Ltd., Melplate Ni-865M, 20 vol% aqueous solution) at 85 ° C. and pH = 4.6 for 20 minutes.
10. Acid immersion: The test substrate was immersed in a 10 vol% sulfuric acid aqueous solution at room temperature for 1 minute.
11. Washing with water: The test substrate was immersed in running water for 30 seconds to 1 minute.
12 Electroless gold plating: The test substrate was immersed for 10 minutes in a gold plating solution of 95 ° C. and pH = 6 (manufactured by Meltex Co., Ltd., an aqueous solution of Ourolectroles UP 15 vol%, potassium gold cyanide 3 wt%).
13. Water washing: The test substrate was immersed in running water for 3 minutes.
14 Hot water washing: The test substrate was immersed in warm water at 60 ° C., thoroughly washed with water for 3 minutes, thoroughly drained and dried.
Through such a process, a test substrate plated with electroless gold was obtained.

(9) Electrical insulation:
The electrical insulation of the cured film was evaluated according to the following criteria. However, only the sample which did not gel was tested.
Humidification conditions: temperature 120 ° C., humidity 85% RH, applied voltage 30 V, 50 hours.
Measurement conditions: measurement time 60 seconds, applied voltage 500V.
○: Insulation resistance value after humidification of 10 ¹⁰ Ω or more, no copper migration Δ: Insulation resistance value after humidification of 10 ¹⁰ Ω or more, copper migration ×: Insulation resistance value after humidification of 10 ⁹ Ω or less, copper migration Yes Test results are shown in Table 10.

Example 8 and Comparative Example 4
Using the epoxy resin reactant solution obtained in Synthesis Example 2 and the carboxyl group-containing photosensitive compound solution obtained in Synthesis Example 3, each component was added according to the composition shown in Table 11 (numerical values are parts by mass). Each curable composition was prepared by mixing and kneading each separately with a three roll mill, and further adding 100 parts of methyl ethyl ketone and stirring. Subsequently, this curable composition is applied on a support, dried by heating, a curable composition layer having a thickness of 20 to 30 μm is formed, a cover film is bonded, and the storage stability of the obtained film is determined. evaluated. Next, the cover film is peeled off, and the film is bonded to the surface-treated copper through-hole printed wiring board on which the pattern is formed. Then, a negative film having a resist pattern is brought into close contact with the support, and an ultraviolet exposure device ) Irradiation with ultraviolet rays (exposure amount: 400 mJ / cm ² ) using Oak Manufacturing Co., Ltd., model HMW-680 GW), peeling off the support, spraying with 1 wt% aqueous sodium carbonate solution for 60 seconds, 2.0 kg / cm ² spray pressure Then, it was cured by heating with a hot air drier at 150 ° C. for 60 minutes to prepare a test substrate. With respect to the test substrate having the obtained cured film, each test of crack resistance, PCT resistance, adhesion, solder heat resistance, acid resistance, alkali resistance, and electroless gold plating resistance was performed by the above-described test method and evaluation method. I did it.
In addition, using a B pattern of a printed circuit board (thickness 1.6 mm) defined by IPC instead of a copper through-hole printed wiring board, a test board was produced under the same conditions as described above, and an electrical insulation resistance test was performed. .
Table 12 shows the results of the above tests.

The evaluation methods of the performance tests for crack resistance, PCT resistance, adhesion, solder heat resistance, acid resistance, alkali resistance, electroless gold plating resistance, and electrical insulation in Table 12 above are (2) to (9 The evaluation method of the test for storage stability is as follows.
(10) Storage stability:
Films of the compositions in Table 11 were stored at 5 ° C. and evaluated according to the following criteria.
○: Development time is within 90 seconds △: Development time is 91 seconds or more ×: Development is impossible

  Since the curable composition of the present invention as described above is excellent in storage stability, can be composed in a one-pack type, and a cured product having excellent properties as described above can be obtained, a solder resist for a printed wiring board can be obtained. In addition, it can be advantageously used as a dry film thereof, as well as an etching resist, a plating resist, an interlayer insulating layer of a multilayer wiring board, a permanent mask used for manufacturing a tape carrier package, a resist for a flexible wiring board, a resist for a color filter It is also useful for applications such as inkjet resists.

Claims (6)

  (A) an epoxy resin having a 1,3-dioxolane ring obtained by partially adding an aldehyde to an epoxy resin having two or more epoxy groups in one molecule, (B) a carboxyl group-containing compound, C) A curable composition comprising a photosensitive (meth) acrylate compound and (D) a photopolymerization initiator.   (A) An epoxy resin having a 1,3-dioxolane ring, obtained by partially adding an aldehyde to an epoxy resin having two or more epoxy groups in one molecule, (B ′) carboxyl group-containing photosensitivity A curable composition comprising a compound and (D) a photopolymerization initiator.   In the said epoxy resin (A), the reaction ratio of the aldehyde with respect to an epoxy resin is 0.03-0.9 equivalent for a carbonyl group with respect to 1 equivalent of epoxy groups, The Claim 1 or 2 characterized by the above-mentioned. Curable composition.   A film comprising: a support; and a layer made of the curable composition according to any one of claims 1 to 3 formed on the support.   The film according to claim 4, further comprising a peelable cover film on the curable composition layer.   Hardened | cured material of the curable composition as described in any one of the said Claims 1 thru | or 3.