JP5164092B2 - Thermosetting composition and cured product thereof - Google Patents

Description

  The present invention relates to a thermosetting composition and a cured product thereof. More specifically, the composition has excellent storage stability, can be composed in a one-pack type, and has excellent properties such as heat resistance and electrical insulation properties. The present invention relates to a thermosetting composition giving a product and a cured product thereof.

  It is conventionally known that a compound having a 1,3-dioxolane ring can be obtained by reacting an epoxy compound with a ketone or an aldehyde using a Lewis acid as a catalyst. For example, a (meth) acrylate compound or allyl ether having a 1,3-dioxolane ring is synthesized by reacting glycidyl (meth) acrylate or allyl glycidyl ether with a ketone or aldehyde in the presence of an acid catalyst such as a Lewis acid. The method to do is described in many patent documents (refer patent documents 1-5), and the obtained compound is a crosslinking monomer for producing a raw material polymer for contact lens production, an ultraviolet curable paint, a photosensitive material, etc. It is taught that it can be used as a component of

  Also, an epoxy compound having two or more epoxy groups in one molecule is reacted with a large excess of ketone in the presence of a Lewis acid catalyst to convert all of the epoxy groups into 1,3-dioxolane rings. Has also proposed a method of synthesizing a compound having two or more 1,3-dioxolane rings in one molecule (see Patent Document 6). This compound is used for a one-component moisture-curable polyurethane resin composition or heat. It is taught that it can be used as a latent curing agent for curable resins.

  However, the compound having a conventionally known 1,3-dioxolane ring as described above is difficult to use as a thermosetting component such as an epoxy resin even though it is a latent curing agent. The composition containing it has excellent properties such as solder heat resistance, electrical insulation, adhesion to various substrates, and electroless gold plating resistance required for solder resists and interlayer insulation layers of printed wiring boards. It is difficult to manufacture things.

  By the way, as a multilayer printed wiring board for electronic devices, a predetermined number of prepregs obtained by impregnating a base material such as glass cloth with an epoxy resin and dicyandiamide and drying are further laminated, and if necessary, copper foil A copper clad laminate produced by laminating a metal foil such as the above on one side or both sides and performing vacuum pressing at a high temperature (around 180 ° C.) for several hours is used. Copper-clad laminates using prepregs impregnated with a thermosetting composition comprising such an epoxy resin and dicyandiamide are required for printed wiring boards such as heat resistance, moisture resistance, crack resistance, and workability. It has characteristics. However, recent multilayer printed wiring boards are required to have high-density mounting, high integration, high-density electrical wiring, lightness, shortness, etc., and it is difficult for copper-clad laminates to meet these requirements. It is.

  On the other hand, recently, a build-up type multilayer printed wiring board in which conductor circuit layers and interlayer insulating layers are alternately stacked has attracted attention. This build-up multilayer printed wiring board uses, as an interlayer insulating layer, a resin composition in which a curing agent or a filler is mixed with an epoxy resin instead of a prepreg. As a method for forming such an interlayer insulating layer, a screen is used. Examples thereof include a printing method, a roll coating method, and a laminating method using a resin film. More recently, multilayer printed wiring boards that have been built up using a resin-coated copper foil that has been semi-cured by previously applying a resin onto the copper foil have also been employed. However, since such a build-up multilayer printed wiring board cannot be vacuum-pressed at a high temperature (around 180 ° C.) in the manufacturing process, a thermosetting composition comprising an epoxy resin and dicyandiamide has a slow reaction and is used. Can not.

Therefore, a composition using a low-temperature fast-curing curing agent system composed of dicyandiamide and an imidazole compound as an epoxy resin has been proposed. However, in such a curing agent system, the imidazole compound decomposes dicyandiamide and reacts rapidly with the epoxy resin. Therefore, it is difficult to stably roughen the surface of the interlayer insulating resin, and therefore, it is impossible to ensure a stable peel strength with the conductor layer, and peeling or the like occurs in the heat resistance test. was there. Moreover, such a curing agent-based composition having a high curing rate at a low temperature has poor storage stability. Therefore, a resin composition used in a usage form such as a film or a copper foil with a resin also requires storage stability in one liquid, but this is a problem.
JP-A-60-155177 (Claims) JP-A-60-161977 (Claims) JP-A-60-208974 (Claims) JP 58-8078 A (Claims) JP 58-39680 A (Claims) Japanese Patent Laid-Open No. 10-139777 (Claims)

  The present invention has been made in view of the problems of the prior art as described above, and its purpose is excellent in storage stability, can be composed in a one-pack type, and has electrical insulation properties and adhesion to various substrates. It is in providing the thermosetting composition and its hardened | cured material from which the outstanding cured film which fully satisfies characteristics, such as property and solder heat resistance, is obtained.

In order to achieve the above object, according to the present invention, (A) one or more epoxy groups in one molecule, an epoxy resin having a structure represented by the following general formula (1), and (B) phenolic There is provided a thermosetting composition comprising a compound having a hydroxyl group and / or a carboxyl group.

(In the formula, R ¹ and R ² may be the same or different, and are each independently a hydrogen atom or a hydrocarbon group having 1 to 17 carbon atoms, or R ¹ and R ² are cyclic. It may be a bonded group.)

According to another aspect of the present invention, (A ′) one or more epoxy groups in one molecule and an epoxy resin (A-1) having a structure represented by the general formula (1) and / or Epoxy resin (A-2) having two or more epoxy groups in one molecule, (B) a compound having a phenolic hydroxyl group and / or a carboxyl group, (C) phosphoric acid, hydrochloric acid, sulfuric acid, phosphotungstic acid, three Thermosetting, characterized by containing at least one acid selected from boron fluoride ether complex, silicotungstic acid, trifluoromethanesulfonic acid, polyphosphoric acid and acidic phosphoric acid ester , and (D) a carbonyl group-containing solvent A composition is provided.

In a preferred embodiment, the epoxy resin having the structure represented by the general formula (1) is a compound containing a carbonyl group in an epoxy resin having two or more epoxy groups in one molecule (hereinafter referred to as a polyfunctional epoxy resin). Is an epoxy resin having a 1,3-dioxolane ring obtained by partial addition reaction, and preferably the reaction ratio of the carbonyl group-containing compound to the polyfunctional epoxy resin is carbonyl to 1 equivalent of epoxy group. The group is 0.03 to 0.9 equivalent.
In any of the above-described embodiments, preferably, (E) a curing accelerator is further contained.

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

The thermosetting composition of the present invention uses an epoxy resin (A-1) having a 1,3-dioxolane ring represented by the general formula (1) instead of a polyfunctional epoxy resin that is generally used conventionally. Or in combination with an acid (C) and a carbonyl group-containing solvent (D) even when a polyfunctional epoxy resin (A-2) conventionally used is used, it has excellent storage stability, Can be composed into molds. In particular, as an epoxy resin, an epoxy resin (A-1) having a 1,3-dioxolane ring obtained by partially adding a carbonyl group-containing compound to a polyfunctional epoxy resin or an ordinary polyfunctional epoxy resin ( In the case of using a mixture with A-2) and using (C) acid and (D) carbonyl group-containing solvent as stabilizers, the composition is more excellent in storage stability and can be easily formed into a one-pack type. Moreover, since it contains the compound (B) which has a phenolic hydroxyl group and / or a carboxyl group as a hardening | curing agent with such an epoxy resin (A-1 and / or A-2), it is thermosetting and multilayer A cured product (cured film) excellent in electrical insulation, adhesion, heat resistance and the like required for an interlayer insulating layer of a printed wiring board can be obtained.
In addition, the thermosetting composition of the present invention is excellent in storage stability, can be composed in a one-pack type, and can produce a dry film excellent in storage stability at 5 ° C. or higher. This is also advantageous.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have obtained 1 represented by the general formula (1), which is obtained by partially adding a carbonyl group-containing compound to a polyfunctional epoxy resin. The reaction ratio of the carbonyl group-containing compound to the epoxy resin (A-1) having a 1,3-dioxolane ring, particularly a polyfunctional epoxy resin, is 0.03 to 0.9 equivalent with respect to 1 equivalent of epoxy group. A combination of an epoxy resin (A-1) having a certain 1,3-dioxolane ring and a compound (B) having a phenolic hydroxyl group and / or a carboxyl group is conventionally used as a polyfunctional epoxy resin Better storage stability than a combination with a compound having a phenolic hydroxyl group and / or a carboxyl group, or as an epoxy resin. Even when a polyfunctional epoxy resin (A-2) that is generally used is used, by further blending an acid (C) and a carbonyl group-containing solvent (D) as a storage stabilizer, the storage stability is excellent. In particular, by using an epoxy resin (A-1) having a 1,3-dioxolane ring and blending an acid (C) and a carbonyl group-containing solvent (D) as a storage stabilizer, the storage stability is further improved. I found. Further, the cured product obtained from such a thermosetting composition is more heat resistant than a cured product of a composition comprising a combination of a normal polyfunctional epoxy resin and a compound having a phenolic hydroxyl group and / or a carboxyl group. Forming a flexible coating without being inferior in properties, and further having excellent properties as described above necessary for solder resists and interlayer insulation layers, with excellent adhesion to the substrate, and completed the present invention It is what led to it.

  That is, the epoxy resin (A-1) having a 1,3-dioxolane ring obtained by partially adding a carbonyl group-containing compound to the polyfunctional epoxy resin contained in the thermosetting composition of the present invention, For example, when the reaction ratio of the carbonyl group-containing compound to the polyfunctional epoxy resin is 0.03 to 0.9 equivalent of the carbonyl group to 1 equivalent of the epoxy group, the unreacted epoxy group, the epoxy group and the carbonyl group It has a structure with a 1,3-dioxolane ring formed by the reaction of the containing compound. (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-opening hardly reacts with the phenolic hydroxyl group and / or carboxyl group. Therefore, the reactivity of the obtained epoxy resin (A-1) having a 1,3-dioxolane ring and the compound (B) having a phenolic hydroxyl group and / or a carboxyl group is that a 1,3-dioxolane ring exists. Even when these coexist, the storage stability is excellent as compared with the case where the original (normal) polyfunctional epoxy resin is used. However, since the 1,3-dioxolane ring is partially formed in the epoxy resin, there is still a sufficient amount of epoxy groups. Therefore, the cured film obtained by the reaction of an epoxy resin having a 1,3-dioxolane ring and a compound having a phenolic hydroxyl group and / or a carboxyl group is an original (normal) polyfunctional epoxy resin and a phenolic hydroxyl group and / or Or it is not inferior to the cured film obtained by reaction with the compound which has a carboxyl group, and is excellent in the above various characteristics.

  The above-described action is not limited to the case of using an epoxy resin (A-1) having a 1,3-dioxolane ring obtained by partially adding a carbonyl group-containing compound to a polyfunctional epoxy resin in advance. Even when a polyfunctional epoxy resin (A-2) conventionally used as an epoxy resin is used, it can also be obtained by blending an acid (C) and a carbonyl group-containing solvent (D) as a storage stabilizer. . That is, since the acid (C) and the carbonyl group-containing solvent (D) coexist with the polyfunctional epoxy resin (A-2) and the compound (B) having a phenolic hydroxyl group and / or a carboxyl group, Test Example 1 described later. As is clear from the results shown in FIG. 1, during storage, the polyfunctional epoxy resin (A-2) contained in the composition partially reacts with the acid (C) and the carbonyl group-containing solvent (D), and 1,3 -A dioxolane ring is formed, and an epoxy resin having a structure in which a part of the epoxy group of the polyfunctional epoxy resin (A-2) has a 1,3-dioxolane ring. Since the 1,3-dioxolane ring inhibits the reaction with a phenolic hydroxyl group or a carboxyl group, the composition does not gel during storage and has excellent storage stability. That is, since the 1,3-dioxolane ring is partially formed in the epoxy resin during storage, the epoxy resin having the formed 1,3-dioxolane ring and the compound having a phenolic hydroxyl group and / or carboxyl group The reactivity is reduced by the presence of the 1,3-dioxolane ring. Therefore, even when an epoxy resin having a 1,3-dioxolane ring and a compound having a phenolic hydroxyl group and / or a carboxyl group coexist in the composition, the storage stability is excellent. However, since the 1,3-dioxolane ring is partially formed in the epoxy resin, there is still a sufficient amount of epoxy groups. Therefore, the cured coating film obtained by the reaction between such an epoxy resin and a compound having a phenolic hydroxyl group and / or a carboxyl group is cured by a reaction between the original (ordinary) epoxy resin and the carboxyl group-containing compound. It is not inferior to a coating film, and is excellent in various properties as described above.

  As mentioned above, it is obtained by using the epoxy resin (A-1) having a 1,3-dioxolane ring as the polyfunctional epoxy resin blended with the compound (B) having a phenolic hydroxyl group and / or a carboxyl group. The storage stability of the thermosetting composition is superior to the case where a normal polyfunctional epoxy resin is used. However, since an epoxy resin having a 1,3-dioxolane ring still has a sufficient amount of epoxy groups, when it is stored at room temperature for a long period of time, it tends to cause a reaction with a carboxyl group-containing compound and gel. . As a result of further study on such a phenomenon, the present inventors have formulated an acid (C) and a carbonyl group-containing solvent (D) into the thermosetting composition containing each of the components as described above. Thus, it has been found that the reaction between an epoxy resin and a compound having a phenolic hydroxyl group and / or a carboxyl group can be further suppressed, and better storage stability can be obtained over a long period of time. That is, when the epoxy resin (A-1) having a 1,3-dioxolane ring and the acid (C) and the carbonyl group-containing solvent (D) coexist, the epoxy resin having the 1,3-dioxolane ring (A-1) The modification of the epoxy group remaining in the 1,3-dioxolane ring does not proceed, and the carbonyl group-containing compound (carbonyl group-containing solvent) is added to the epoxy group (the state modified to the 1,3-dioxolane ring) In parallel with the free state, in other words, the carbonyl group-containing solvent can act as a stabilizer for the epoxy resin by coexisting with the acid, and can exhibit excellent storage stability.

  As described above, whether or not to use an epoxy resin (A-1) having a 1,3-dioxolane ring obtained by partially adding a carbonyl group-containing compound to a polyfunctional epoxy resin as an epoxy resin is used. Regardless of whether or not the polyfunctional epoxy resin (A-2) having two or more epoxy groups in one molecule is used or a combination thereof is used, the above-described action is not caused in the composition. It is exhibited if (C) and the carbonyl group-containing solvent (D) are present. However, carbonyl group-containing solvents such as ketones are more easily evaporated at room temperature than at low temperatures (for example, about 5 ° C.). Therefore, if the carbonyl group-containing solvent is stored in a state where it does not evaporate, it can be stored for a very long time. For example, in the case of a liquid thermosetting composition, if sealed in a container, it will not gel even after long-term storage at room temperature for more than half a year. In the case of a dry film, for example, it is not gelled by long-term storage at room temperature for half a year or more by storing it in a vacuum pack.

  As described above, the epoxy resin (A-1) having a 1,3-dioxolane ring and the compound (B) having a phenolic hydroxyl group and / or a carboxyl group, or having a 1,3-dioxolane ring (A-1) and / or a normal polyfunctional epoxy resin (A-2), a compound (B) having a phenolic hydroxyl group and / or a carboxyl group, an acid (C) and a carbonyl group-containing solvent (D) The thermosetting composition of the present invention preferably further containing a curing accelerator (E) is excellent in storage stability, can be composed in a one-pack type, and exhibits excellent thermosetting properties. At the same time, by curing the coating film, a cured product excellent in electrical insulation, adhesion, solder heat resistance, and the like can be obtained.

Hereinafter, each component of the thermosetting composition of this invention is demonstrated in detail.
First, the epoxy resin (A-1) 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 a carbonyl group-containing compound using an acid as a catalyst. Can be obtained. The reaction ratio of the carbonyl group-containing compound to the polyfunctional epoxy resin is 0.03 to 0.9 equivalent, preferably 0.05 to 0.8 equivalent, more preferably carbonyl group to 1 equivalent of epoxy group. Is 0.1 to 0.7 equivalent, particularly preferably 0.2 to 0.5 equivalent.

  As the polyfunctional epoxy resin, any polyfunctional epoxy resin having two or more epoxy groups in one molecule can be used, and is not limited to a specific polyfunctional epoxy resin. Specific examples of the polyfunctional epoxy resin include JER828, JER834, JER1001, JER1004 manufactured by Japan Epoxy Resins Co., Ltd., Epicron 840, Epicron 850, Epicron 1050, Epicron 1050, Epitolon 2055, Toto Kasei Co., Ltd. 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.E. 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. 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 the carbonyl group-containing compound, a ketone or an aldehyde can be preferably used.
As ketones, acetone, methyl ethyl ketone, methyl n-propyl ketone, methyl isobutyl ketone, methyl n-butyl ketone, methyl n-amyl ketone, ethyl benzyl ketone, di-n-amyl ketone, n-hexyl benzyl ketone, cyclohexanone, acetophenone And benzoin.

Examples of the aldehyde include aliphatic saturated aldehydes such as acetaldehyde, propionaldehyde, butyraldehyde, valeraldehyde, piperine aldehyde, capronaldehyde, caprylaldehyde, tridecylaldehyde, myristic aldehyde, pentadecylaldehyde, palmitic aldehyde, stearaldehyde; Aliphatic unsaturated aldehydes such as acrolein, crotonaldehyde, propiolaldehyde, aromatic aldehydes such as benzaldehyde, 0-, m-, or p-tolualdehyde, salicylaldehyde, cinnamaldehyde, α- or β-naphthaldehyde; furfural And the like, and the like.
Of these carbonyl group-containing compounds, ketones, particularly acetone, are preferred.

  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 acids such as triphosphoric acid, trimetaphosphoric acid, and tetrametaphosphoric acid. Acid phosphates such as acid, methyl acid phosphate, isodecyl acid phosphate, oleyl acid phosphate, and the like can be mentioned. Among these, inorganic acids and boron trifluoride ether complexes are preferable from the viewpoint of yield, From the viewpoint of electronic materials, phosphoric acid and acidic phosphoric acid esters, particularly phosphoric acid are preferred. 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 carbonyl group-containing compound is unfavorable.

  The reaction between the polyfunctional epoxy resin and the carbonyl group-containing compound is preferably performed in a carbonyl group-containing solvent such as a ketone or an aldehyde, but the ketone and another solvent, for example, a mixed solvent of ketone and toluene, A mixed solvent with carbitol can 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.

As the compound (B) having a phenolic hydroxyl group and / or carboxyl group, a compound having two or more phenolic hydroxyl groups and / or carboxyl groups in one molecule can be preferably used, and is limited to a specific compound. It is not something.
Examples of the phenolic hydroxyl group-containing compound include phenol novolak resins (for example, HF-1 manufactured by Meiwa Kasei Co., Ltd.), aralkylphenol resins (for example, XL225 manufactured by Mitsui Chemicals, Inc.), terpene phenol resins (for example, Japan Epoxy Resin ( Epure MP402), naphthol modified phenolic resin (for example, Kayacure NHN manufactured by Nippon Kayaku Co., Ltd.), dicyclopentadiene modified phenolic resin (for example, DDP-M manufactured by Nippon Petrochemical Co., Ltd.), bisphenol A type Novolak phenol resin (for example, BPA-D manufactured by Meiwa Kasei Co., Ltd.), aminotriazine novolak resin (for example, ATN resin manufactured by Dainippon Ink & Chemicals, Inc.), 10- (2,5-dihydroxyphenyl) -10H- Oxa-phosphenanthrene = 10-oxide ( Eg to the Sanko Co. HCA-HQ) known phenol resins, such as may be used alone or in combination of two or more.

  Examples of the carboxyl group-containing compound include succinic acid, sebacic acid, maleic anhydride, thiomalic acid, terephthalic acid, phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, methylhexa Known carboxylic acids such as hydrophthalic anhydride, naphthalenedicarboxylic acid, p-hydroxybenzoic acid, trimellitic acid, trimellitic anhydride, and pyromellitic anhydride can be used, but are not limited thereto.

  The carboxyl group-containing compound includes (1) unsaturated carboxylic acid (a) such as (meth) acrylic acid, and unsaturated double carboxylic acid such as styrene, α-methylstyrene, lower alkyl (meth) acrylate, and isobutylene. A carboxyl group-containing compound obtained by copolymerizing a compound (b) having a bond; (2) an epoxy group of a copolymer of a compound (b) having an unsaturated double bond and glycidyl (meth) acrylate; Two organic acids (c) having one carboxyl group in one molecule such as an alkyl carboxylic acid of 2 to 17 and an aromatic group-containing alkyl carboxylic acid and having no ethylenically unsaturated bond are produced to react with each other. A saturated or unsaturated polybasic acid anhydride (d) such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, etc. Carboxyl group-containing compounds obtained can be used a polymer compound and the like.

  Further, the carboxyl group-containing compound includes (1) a copolymer of an unsaturated carboxylic acid (a) and a compound (b) having an unsaturated double bond, a vinyl group, an allyl group, (meth) Obtained by reacting a compound (e) having an ethylenically unsaturated group such as an acryloyl group and a reactive group such as an epoxy group or an acid chloride, such as glycidyl (meth) acrylate, and adding the ethylenically unsaturated group as a pendant. Carboxyl group-containing photosensitive compound; (2) a compound having an unsaturated double bond with an epoxy group such as glycidyl (meth) acrylate and α-methylglycidyl (meth) acrylate (f) and a compound having an unsaturated double bond The copolymer of (b) is reacted with an unsaturated carboxylic acid (a), and the resulting secondary hydroxyl group is saturated or unsaturated polybasic acid anhydride (d (3) Compound (b) having an unsaturated double bond (g) and an acid anhydride (g) having an unsaturated double bond such as maleic anhydride and itaconic anhydride A carboxyl group-containing photosensitive compound obtained by reacting a copolymer (h) with a hydroxyl group such as hydroxyalkyl (meth) acrylate with an unsaturated double bond; (4) in one molecule as described above Esterification reaction (total esterification or partial esterification) of an epoxy group of a polyfunctional epoxy compound (i) having at least two epoxy groups and a carboxyl group of an unsaturated monocarboxylic acid (j) such as (meth) acrylic acid Carboxyl group-containing photosensitive compound obtained by reacting saturated or unsaturated polybasic acid anhydride (d) with the resulting hydroxyl group. Things can also be used. When such a carboxyl group-containing photosensitive compound is used, not only a curing reaction between an epoxy group and a carboxyl group, but also heat curing by a thermal radical can be expected due to the presence of an unsaturated double bond.

  The compound (B) having a phenolic hydroxyl group and / or a carboxyl group as described above may be used in several kinds as a curing agent at the same time. The blending amount is 5 to 500 parts by mass, preferably 10 to 300 parts by mass with respect to 100 parts by mass of the epoxy resin (A-1 and / or A-2) (total amount or single amount when used alone). The proportion of parts is appropriate.

The acid (C) and the carbonyl group-containing solvent (D) are mainly used as a storage stabilizer as described above.
As the acid (C), an inorganic acid, an organic acid, an acidic phosphoric acid ester, or the like similar to the acid catalyst used when the carbonyl group-containing compound is partially added to the polyfunctional epoxy resin can be used. Among these, phosphoric acid and acidic phosphoric acid ester are preferable from the viewpoint of electronic materials. The amount of the acid used is preferably 0.001% by mass to 20% by mass with respect to the epoxy resin (A-1 and / or A-2), more preferably 0.01 to 10% by mass. %, Particularly preferably 0.1 to 7% by mass. If the ratio of the acid exceeds 20% by mass, the composition may be gelled. On the other hand, if it is less than 0.001% by mass, the effect of storage stability is hardly obtained, which is not preferable.

  Examples of the carbonyl group-containing solvent (D) include acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl isobutyl ketone, methyl-n-butyl ketone, methyl-n-amyl ketone, ethyl benzyl ketone, di-n-amyl ketone, and n-hexyl. Examples include ketone solvents such as benzyl ketone, cyclohexanone, acetophenone, and benzoin, and aldehyde solvents such as propionaldehyde and butyraldehyde. Among these, ketone solvents are preferable. These carbonyl group-containing solvents can be used alone or as a mixture of two or more. 5 mass parts or more is suitable for the compounding quantity with respect to 100 mass parts (total quantity or single quantity in the case of individual use) of the said epoxy resin (A-1 and / or A-2). When the amount of the carbonyl group-containing solvent (F) is less than 5 parts by mass, the effect of storage stability is hardly obtained, which is not preferable.

  Examples of the curing accelerator (E) 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-dimethyl Amine compounds such as benzylamine and 4-methyl-N, N-dimethylbenzylamine; hydrazine compounds such as adipic hydrazide and sebacic acid hydrazide; and phosphorus compounds such as triphenylphosphine can be preferably used. Examples of commercially available products include 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (both trade names of imidazole compounds) manufactured by Shikoku Kasei Kogyo Co., Ltd., U-CAT3503N manufactured by San Apro 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. Particularly, in order to improve thermosetting properties, the present invention is not limited to these, and a reaction between a curing catalyst for a compound having a cyclic ether or a compound having a cyclic ether and a compound having a phenolic hydroxyl group and / or a carboxyl group. It may be used as long as it promotes, and it may be used alone or in admixture of two or more. Guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-4,6-diamino-S-triazine, 2 S-triazine derivatives such as -vinyl-4,6-diamino-S-triazine / isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine / isocyanuric acid adduct can also be used, Preferably, these compounds are used in combination with the curing accelerator.

  Further, as a curing accelerator (E), benzoyl peroxide, acetyl peroxide, methyl ethyl ketone peroxide, lauroyl peroxide, dicumyl peroxide, di-t-butyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide Organic peroxides such as 2,2′-azobisisobutyronitrile, 2,2′-azobis-2-methylbutyronitrile, 2,2′-azobis-2,4-divaleronitrile, 1, 1′-azobis (1-acetoxy-1-phenylethane), 1′-azobis-1-cyclohexanecarbonitrile, dimethyl-2,2′-azobisisobutyrate, 4,4′-azobis-4-cyanovalic Acid, 2-methyl-2,2′-azobispropanenitrile and other azo initiators Also the thermal radical polymerization initiators may be used alone or in combination of two or more. In addition, when using an organic peroxide having a low curing rate as a thermal radical polymerization initiator, a tertiary amine such as tributylamine, triethylamine, dimethyl-p-toluidine, dimethylaniline, triethanolamine, diethanolamine, Or metal soaps, such as cobalt naphthenate, cobalt octenoate, manganese naphthenate, can be used together as an accelerator.

  The compounding quantity of the said hardening accelerator (E) is enough with a normal quantitative ratio, for example, when 100 parts by mass (total amount or single use) of the epoxy resin (A-1 and / or A-2) A ratio of 0.1 to 20 parts by mass, preferably 0.5 to 15.0 parts by mass, is appropriate for the single amount).

Further, the thermosetting composition of the present invention comprises the epoxy resin (A-1 and / or A-2), the compound (B) having a phenolic hydroxyl group and / or a carboxyl group, or further a curing accelerator (E). In addition, an organic solvent can be added to adjust the composition to a viscosity suitable for the coating method.
Examples of the organic solvent include aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether , Glycol ethers such as 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 acetate, diethylene glycol Monoethyl ether Acetates such as cetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate and dipropylene glycol monomethyl ether acetate; alcohols such as ethanol, propanol, ethylene glycol and propylene glycol; aliphatic hydrocarbons such as octane and decane; petroleum Examples include petroleum solvents such as 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.

  Furthermore, the thermosetting composition of this invention can mix | blend the compound which has a 2 or more cyclic ether in 1 molecule 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 oxetane compounds and oxolane compounds.

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.

  Further, the thermosetting composition of the present invention contains a phenoxy resin which is a condensate of epichlorohydrin and various bifunctional phenolic compounds or a hydroxyl group of the hydroxy ether moiety present in the skeleton at a quantitative ratio that does not impair the effects of the present invention. Thermoplastic resins such as phenoxy resins esterified using various acid anhydrides and acid chlorides, polyimide resins, polyamideimide resins, polyphenol resins, polycyanate resins, polyester resins, thermosetting polyphenylene ether resins, or the like An organic filler can also be added.

  The thermosetting composition of the present invention may further contain barium sulfate, barium titanate, amorphous silica, crystalline silica, fused silica, spherical silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide as necessary. In addition, known 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 quantity of an inorganic filler is 10-300 mass parts with respect to 100 mass parts (total quantity or single quantity in the case of single use) of the said epoxy resin (A-1 and / or A-2), Preferably it is 30. A proportion of ~ 200 parts by weight is appropriate.

  In addition, the thermosetting composition of the present invention may further include known and commonly used colorants such as phthalocyanine blue, phthalocyanine green, iodin green, disazo yellow, crystal violet, titanium oxide, carbon black, and naphthalene black. , Hydroquinone, hydroquinone monomethyl ether, t-butylcatechol, pyrogallol, phenothiazine, and other known and conventional thermal polymerization inhibitors, finely divided silica, organic bentonite, montmorillonite, and other known and commonly used thickeners, silicones, fluorines, and polymers Known and conventional additives such as antifoaming agents and / or leveling agents such as silane coupling agents such as imidazole, thiazole, and triazole can be blended.

  Furthermore, the thermosetting composition of the present invention may contain a flame retardant such as a halogen flame retardant, a phosphorus flame retardant, and an antimony flame retardant as needed for the purpose of obtaining flame retardancy. The compounding amount of the flame retardant is usually 1 to 200 parts by mass, preferably 100 parts by mass of the epoxy resin (A-1 and / or A-2) (total amount or single amount when used alone), preferably 5 to 50 parts by mass. 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.

  The form of the thermosetting composition of the present invention may be provided as a coating material whose viscosity is appropriately adjusted, or may be a dry film obtained by applying the thermosetting composition on a support and drying the solvent. Good. Furthermore, it is good also as a prepreg sheet | seat by making it apply | coat and / or impregnate to sheet-like fiber base materials, such as glass cloth, glass, and an aramid nonwoven fabric, and making it semi-harden.

  When the coating material, dry film, or prepreg using the thermosetting composition of the present invention is used as an insulating layer of a multilayer printed wiring board, in the case of a coating material, the inner layer circuit board on which the circuit is formed is directly coated. , Drying and curing. In the case of a dry film, the dry film may be heat laminated to the inner layer circuit board and integrally formed, and then cured in an oven or cured by a hot plate press. In the case of a prepreg, it is placed on an inner circuit board, sandwiched between metal plates through a release film, and pressed by pressing and heating.

  When the thermosetting composition of the present invention is in the form of a dry film comprising a support and a layer made of the thermosetting composition formed on the support, preferably the heat of the film A peelable cover film is further laminated on the curable composition layer. 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. Further, release paper, copper foil, metal foil such as aluminum foil, and the like can be used. The support may be subjected to mud treatment, corona treatment, mold release treatment, and the like. Here, the thickness of the support is not particularly limited, but is preferably selected in the range of 10 to 150 μm.

  The thermosetting composition layer on the support has a uniform thickness on the support with a comma coater, blade coater, lip coater, rod coater, squeeze coater, reverse coater, transfer roll coater, etc. Although it is obtained by applying, heating and drying to volatilize the solvent, the thickness is not particularly limited, but it is preferably selected in 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 thermosetting composition layer and the cover film is smaller than the adhesive force between the thermosetting composition layer and the support.

  The thermosetting composition of the present invention having the above composition can be used as an adhesive or sealant in various technical fields, or as a molding material. It can be suitably used as an interlayer insulating layer of a wiring board. For example, the thermosetting composition of the present invention is diluted as necessary and adjusted to a viscosity suitable for the application method, and this is applied to, for example, a screen printed method, a curtain coat method, a spray on a printed wiring board formed with a circuit. A tack-free coating film can be formed by coating by a coating method, a 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. In the case of a dry film comprising a support and a layer made of the thermosetting composition formed on the support, it is bonded to a printed circuit board on which a circuit is formed using a hot roll laminator or the like. A coating film can be formed on a printed wiring board on which a circuit is formed by bonding the thermosetting composition layer and the printed wiring board on which a circuit is formed. In the case of a dry film provided with a peelable cover film on the thermosetting composition layer of the film, after peeling the cover film, the thermosetting composition layer and the printed wiring board formed with a circuit are A film can be formed on a printed wiring board on which a circuit is formed by laminating using a hot roll laminator or the like so as to come into contact. Thereafter, by heating and curing, a cured film excellent in electrical insulation, PCT (pressure cooker test) resistance, adhesion, solder heat resistance, chemical resistance, electroless gold plating resistance, and the like is formed.

  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 novolac type epoxy resin (Epototo YDCN-704 manufactured by Toto Kasei Co., Ltd., epoxy equivalent 200 g / eq.) And 100 parts of acetone Was stirred at 20 to 25 ° C., and the epoxy resin was dissolved in acetone. Next, a mixed solution of 2 parts of 85% phosphoric acid and 40 parts of acetone was gradually added dropwise and reacted at 20 to 25 ° C. for 20 hours. Thereafter, the liquid temperature was raised to 40 to 45 ° C. and reacted for 4 hours. The nonvolatile equivalent was 62% and the solid content epoxy equivalent was 226 g / eq. A reaction solution was obtained. The reaction ratio of the ketone to the starting epoxy resin was about 0.09 equivalent of carbonyl group to 1 equivalent of epoxy group.

Synthesis example 2
In a reaction vessel equipped with a stirrer, a thermometer, and a dropping funnel for continuous dripping, 185 parts of a novolac type epoxy resin (RE-306 manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 185 g / eq.) And 92. acetone. 5 parts were charged and stirred at 20 to 25 ° C. to dissolve the epoxy resin in acetone. Next, a mixed solution of 1.85 parts of 85% phosphoric acid and 37 parts of acetone was gradually added dropwise and reacted at 20 to 25 ° C. for 20 hours. Thereafter, the liquid temperature was raised to 40 to 45 ° C. and reacted for 4 hours to obtain a nonvolatile content of 64% and a solid content epoxy equivalent of 201 g / eq. A reaction solution was obtained. The reaction ratio of the ketone to the starting epoxy resin was about 0.06 equivalent of carbonyl group to 1 equivalent of epoxy group.

Synthesis example 3
In a reaction vessel equipped with a stirrer, a thermometer, and a dropping funnel for continuous dripping, 185 parts of bisphenol type epoxy resin (JER828, Japan Epoxy Resin Co., Ltd., epoxy equivalent 185 g / eq.) And 92.5 parts of acetone Was stirred at 20 to 25 ° C., and the epoxy resin was dissolved in acetone. Next, a mixed solution of 1.85 parts of 85% phosphoric acid and 37 parts of acetone was gradually added dropwise and reacted at 20 to 25 ° C. for 20 hours. Thereafter, the liquid temperature was raised to 40 to 45 ° C., the reaction was performed for 4 hours, and the epoxy equivalent of 214 g / eq. A reaction solution was obtained. The reaction ratio of the ketone to the starting epoxy resin was about 0.1 equivalent of carbonyl group to 1 equivalent of epoxy group.

Synthesis example 4
In a reaction vessel equipped with a stirrer, a thermometer, and a dropping funnel for continuous dripping, 185 parts of a novolac type epoxy resin (RE-306 manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 185 g / eq.) And propionaldehyde 92 .5 parts was charged and stirred at 20 to 25 ° C. to dissolve the epoxy resin in propionaldehyde. Next, a mixed solution of 1.85 parts of 85% phosphoric acid and 37 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. The nonvolatile content was 64%, the solid epoxy content was 205 g / eq. A reaction solution was obtained. The reaction ratio of propionaldehyde to the starting epoxy resin was about 0.08 equivalent of carbonyl group per equivalent of epoxy group.

Synthesis example 5
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.

Examples 1 to 10 and Comparative Examples 1 to 3
Each component was mix | blended according to the compounding composition shown in Table 1 (a numerical value is a mass part), it stirred, each thermosetting composition was prepared, and storage stability was evaluated. Next, this thermosetting composition was applied onto a support and dried by heating to form a thermosetting composition layer having a thickness of 20 to 30 μm, and a cover film was bonded to obtain a dry film. Thereafter, the cover film is peeled off, the film is bonded to the surface-treated copper through-hole printed wiring board that has been patterned, and then the support is peeled off and dried in a hot air dryer at 80 ° C. for 30 minutes, and then Heat curing was performed for 60 minutes in a hot air dryer at 150 ° C. to prepare a test substrate. About the test substrate which has the obtained cured film, each test of adhesiveness and solder heat resistance was done with the test method and evaluation method mentioned later.
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 stored at 40 ° C. and evaluated according to the following criteria.
○: not gelled Δ: slightly gelled ×: completely gelled Table 2 shows the test results.

(2) 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, the test was conducted only for those that did not gel.
○: 100/100 with no peeling Δ: 50/100 to 90/100
X: 0/100 to 50/100
The test results are shown in Table 3.

(3) 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, the test was conducted only for those that did not gel.
○: No change in appearance △: Discoloration of the cured film is observed ×: The cured film is floated, peeled off, and solder is submerged. Table 4 shows the test results.

(4) Electrical insulation:
The electrical insulation of the cured film was evaluated according to the following criteria. However, the test was conducted only for those that did not gel.
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 5.

Test example 1
Using the carboxyl group-containing photosensitive compound obtained in Synthesis Example 5, each component was blended according to the formulation shown in Table 6 below and stirred to prepare each thermosetting composition of Formulation Examples A and B.
Each obtained thermosetting composition was allowed to stand at room temperature and 50 ° C. for 7 days, respectively, and the relationship between the acid value and the epoxy equivalent was examined. The results are shown in Table 7. In the case of Formulation Example B containing phosphoric acid, gelation did not occur even after standing for 7 days at room temperature and 50 ° C., respectively. On the other hand, in the case of Formulation Example A not containing phosphoric acid, it did not gel after standing for 7 days at room temperature, but almost gelled after standing for 7 days at 50 ° C., so the sample was dissolved in butyl cellosolve and the acid value When measuring and when measuring the epoxy equivalent by dissolving in chloroform, a portion having a low degree of gelation attached to the wall surface of the container was sampled.

As is clear from the results shown in Table 7 above, in the composition not containing phosphoric acid (Formulation Example A), the acid value decreased when left at 50 ° C. and the epoxy equivalent increased when left at room temperature. That is, this means that the carboxylic acid and the epoxy resin reacted, whereby the acid value decreased and gelled. On the other hand, in the composition containing the phosphoric acid (Prescription Example B), the acid value did not change between standing at room temperature and standing at 50 ° C., and the epoxy equivalent increased. This is because some epoxy groups were changed to 1,3-dioxolane ring by acetone and phosphoric acid, and it was not gelled because the reaction between carboxylic acid and epoxy resin was inhibited by it. Conceivable. Therefore, it can be seen from the results of the above Formulation Example B that a one-component thermosetting composition can be prepared.

  Since the thermosetting 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 printed wiring board solder is obtained. Not only can it be advantageously used as a resist and its dry film, but it is also useful for applications such as interlayer insulating layers of multilayer wiring boards, permanent masks used in the production of tape carrier packages, and resists for inkjets.

Claims (8)

(A) One molecule contains one or more epoxy groups, an epoxy resin having a structure represented by the following general formula (1), and (B) a compound having a phenolic hydroxyl group and / or a carboxyl group. A thermosetting composition characterized.

(In the formula, R ¹ and R ² may be the same or different, and are each independently a hydrogen atom or a hydrocarbon group having 1 to 17 carbon atoms, or R ¹ and R ² are cyclic. It may be a bonded group.) (A ′) One or more epoxy groups in one molecule and an epoxy resin (A-1) having a structure represented by the following general formula (1) and / or two or more epoxy groups in one molecule Epoxy resin (A-2), (B) Compound having phenolic hydroxyl group and / or carboxyl group, (C) Phosphoric acid, hydrochloric acid, sulfuric acid, phosphotungstic acid, boron trifluoride ether complex, silicotungstic acid, trifluoromethane A thermosetting composition comprising at least one acid selected from sulfonic acid, polyphosphoric acid and acidic phosphoric acid ester , and (D) a carbonyl group-containing solvent.
(In the formula, R ¹ and R ² may be the same or different, and are each independently a hydrogen atom or a hydrocarbon group having 1 to 17 carbon atoms, or R ¹ and R ² are cyclic. It may be a bonded group.)   An epoxy resin having a structure represented by the general formula (1) is obtained by partially adding a carbonyl group-containing compound to an epoxy resin having two or more epoxy groups in one molecule. The thermosetting composition according to claim 1 or 2, which is an epoxy resin having a dioxolane ring.   In the epoxy resin having the structure represented by the general formula (1), the reaction ratio of the carbonyl group-containing compound to the epoxy resin is 0.03 to 0.9 equivalent of the carbonyl group with respect to 1 equivalent of the epoxy group. The thermosetting composition according to claim 3.   Furthermore, (E) hardening accelerator is contained, The thermosetting composition as described in any one of the Claims 1 thru | or 4 characterized by the above-mentioned.   A film comprising: a support; and a layer made of the thermosetting composition according to any one of claims 1 to 5 formed on the support.   The film according to claim 6, further comprising a peelable cover film on the thermosetting composition layer.   Hardened | cured material of the thermosetting composition as described in any one of the said Claims 1 thru | or 5.