Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
  • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/26—Processing photosensitive materials; Apparatus therefor
  • G03F7/40—Treatment after imagewise removal, e.g. baking
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K3/00—Apparatus or processes for manufacturing printed circuits
  • H05K3/22—Secondary treatment of printed circuits
  • H05K3/28—Applying non-metallic protective coatings
  • H05K3/285—Permanent coating compositions
  • H05K3/287—Photosensitive compositions

Definitions

• the present invention relates to a curable composition used for 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 is resistant to cracks, electricity. Photo-curing property that gives a cured product with excellent properties such as insulation, PCT (pressure-tucker test) resistance, adhesion to various substrates, solder heat resistance, chemical resistance, and electroless gold adhesion resistance
• the present invention relates to a thermosetting composition and a cured product thereof.
• curable resin compositions used as resists for printed wiring boards are mainly alkali-developable curable compositions using dilute aqueous alkali solutions as a developer in consideration of environmental issues. Yes.
• Examples of such an alkali development type curable composition include 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, and a photopolymerization initiator.
• a composition comprising a photopolymerizable monomer and a polyfunctional epoxy resin having two or more epoxy groups in one molecule (see Patent Document 1), a polyfunctional epoxy compound, and a phenolic group having a hydroxyl group-containing substituent.
• 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 two phenols in one molecule
• An alcoholic secondary hydroxyl group obtained by reacting with an aromatic alcohol resin having a rutile hydroxyl group is reacted with epi-halohydrin, and the resulting reaction product is mixed with an unsaturated group-containing monocarboxylic acid and then an acid anhydride.
• a curable resin obtained by addition, a photopolymerization initiator, a polyfunctional epoxy resin or a composition containing a photosensitive (meth) acrylate compound (see Patent Documents 3 and 4), novolak type
• the reaction product of a phenol resin and an alkylene oxide is reacted with an unsaturated group-containing monocarboxylic acid, and a polybasic acid anhydride is added to the resulting reaction product.
• Carboxy group-containing photosensitive resin obtained by reaction, photopolymerization initiator, polyfunctional epoxy resin, or curable composition containing a photosensitive (meth) acrylate compound (see, for example, Patent Document 5), etc. Is mentioned.
• curable compositions 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.
• a conventional curable composition usually contains a polyfunctional epoxy resin having two or more epoxy groups as a thermosetting component in order to improve solder heat resistance and the like.
• RU because this polyfunctional epoxy resin is highly reactive, curable compositions containing it tend to thicken before application to circuit board blanks with a short shelf life. It is difficult to make a one-component composition.
• 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 mixed with a curing accelerator or the like is mixed, and these are mixed in use.
• a curing agent solution mainly composed of a polyfunctional epoxy resin
• a main agent solution mainly composed of a photosensitive prepolymer and mixed with a curing accelerator or the like
• a curable composition comprising an unsaturated group-containing polycarboxylic acid resin, a diluent, a photopolymerization initiator, and an arylalkylimide compound
• a curable composition comprising a carboxyl group-containing compound, 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, at present, none of these have yet satisfied both the storage stability and various properties required for solder resist.
• Patent Document 1 Japanese Patent Application Laid-Open No. 61-243869
• Patent Document 2 Japanese Patent Application Laid-Open No. 11-288091
• Patent Document 3 Japanese Patent Laid-Open No. 5-32746
• Patent Document 4 International Publication WO 01 / 53375A1
• Patent Document 5 International Publication WO 02 / 024774A1 Publication
• Patent Document 6 Japanese Patent Laid-Open No. 9-278849
• Patent Document 7 Japanese Patent Laid-Open No. 3-191352
• the present invention has been made in view of the above-described problems of the prior art, and the object thereof is excellent in storage stability, can be composed in a one-pack type, and has crack resistance and electrical insulation. Curability that provides an excellent cured film that fully satisfies the properties such as resistance, PCT (pressure-tucker test) resistance, adhesion to various substrates, solder heat resistance, chemical resistance, and electroless gold adhesion resistance. It is to provide a composition.
• PCT pressure-tucker test
• a curable composition characterized in that it contains an attareito toy compound and (F) a photopolymerization initiator.
• the composition contains ( ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ′) a carboxyl group-containing photosensitive compound, ( ⁇ ) an epoxy resin, (C) an acid, (D) a ketone solvent, and (F) a photopolymerization initiator.
• a curable composition characterized by the above.
• the epoxy resin ( ⁇ ) comprises (B-1) an epoxy resin having two or more epoxy groups in one molecule (hereinafter referred to as a polyfunctional epoxy resin) and ( ⁇ _2). It consists of at least one selected from the group consisting of epoxy resins having a 1,3_dioxolane ring obtained by partially adding a ketone to a polyfunctional epoxy resin.
• the reaction ratio of the ketone to the epoxy resin should be 0.03 to 0.9 equivalent of the carbonyl group to 1 equivalent of the epoxy group. preferable.
• the carboxyl group-containing photosensitive compound ( ⁇ ′) includes a compound (a) having two or more epoxy groups in one molecule and an unsaturated group-containing monocarboxylic acid.
• a carboxyl group-containing photosensitive compound ( ⁇ ′-1) obtained by reacting a basic acid anhydride (f), or a compound (g) having 3 or more phenolic hydroxyl groups in one molecule and an alkylene group.
• reaction product (j) with xoxide (h) and / or cyclic carbonate (i) is reacted with unsaturated group-containing monocarboxylic acid (b), and the resulting reaction product (k) is polybasic acid anhydride. It is a carboxyl group-containing photosensitive compound ( ⁇ ′ — 2) obtained by reacting the product (f), or a mixture thereof.
• the carboxyl group-containing photosensitive compound ( ⁇ ') comprises a compound (a) having two or more epoxy groups in one molecule, and an unsaturated group-containing monocarboxylic acid. (b), or a reaction product (e) of an unsaturated group-containing monocarboxylic acid (b) and a mixture (d) of a compound (c) having a reactive group that reacts with an epoxy group,
• a carboxyl group-containing photosensitive compound ( ⁇ '-1) obtained by reacting the product (f), a novolac-type phenol resin (g '), an alkylene oxide (h) and / or a cyclic carbonate (i) Carboxyl group obtained by reacting the reaction product (j) with an unsaturated group-containing monocarboxylic acid (b) and reacting the resulting reaction product (k) with a polybasic acid anhydride (f). It is a mixture with the photosensitive resin ( ⁇ '-2).
• the curable composition may be in a liquid form or a so-called dry film.
• a film comprising a support and a layer made of the curable composition formed on the support.
• a film provided with a peelable cover film on the curable composition layer of the film.
• a cured product obtained using the curable composition is provided.
• the curable composition of the present invention has a storage stability by adding an acid (C) and a ketone solvent (D) to an alkali development type epoxy resin-containing curable composition generally used conventionally. It has excellent qualitative properties and can be composed in a one-pack type.
• epoxy resin ( ⁇ ) multifunctional An epoxy resin (B-2) with 1,3-dioxolane ring obtained by partial addition reaction of a ketone with an epoxy resin or a mixture of this with an ordinary polyfunctional epoxy resin (B-1)
• the composition is more excellent in storage stability and can be easily formed into a one-pack type.
• the curable composition of the present invention comprises, together with the epoxy resin (B), a carboxyl group-containing compound (A) and a photosensitive (meth) acrylate compound (E), or a carboxyl group-containing photosensitive compound ( ⁇ ). ') And a photopolymerization initiator (F), so that it is photo-curing and thermosetting, and since the component ( ⁇ ) or component ( ⁇ ,) has a carboxyl group, Development is possible with an aqueous alkali solution. Therefore, the use of the curable composition of the present invention sufficiently satisfies the characteristics such as the electrical insulation and PCT resistance required for a high-density printed circuit board and a resist that can be used for surface mounting. In addition, a cured film with excellent crack resistance, adhesion to various substrates, heat resistance, chemical resistance, and electroless tackiness can be obtained, and a fine film pattern can be easily formed. is there.
• the curable composition of the present invention is excellent in storage stability, a photosensitive dry film excellent in room temperature storage at o ° c or higher can be produced by using this composition. Power S can be. Therefore, the curable composition of the present invention is advantageous in terms of workability in the production of a printed wiring board.
• the present inventors have used, as the epoxy resin ( ⁇ ), an epoxy resin ( ⁇ _2) having a 1,3-dioxolane ring obtained by partially adding a ketone to a polyfunctional epoxy resin, particularly a polyfunctional epoxy resin.
• the reaction ratio of ketone to resin is equivalent to epoxy resin ( ⁇ -2) having 1,3-dioxolane ring in which carbonyl group is 0 ⁇ 03-0.9 equivalent to 1 equivalent of epoxy group and carboxyl group.
• the epoxy resin (B) particularly a polyfunctional epoxy resin having a 1,3_dioxolane ring obtained by partial addition reaction of a ketone.
• the curable composition containing the chemical compound ( ⁇ ′) and the photopolymerization initiator (F) is composed of a normal carboxyl group-containing compound ( ⁇ and / or A ′), an epoxy resin ( ⁇ ), and a photosensitive (meta )
• the composition comprising the attalate compound (ii) and the photopolymerization initiator (F) it forms a flexible coating film that is not inferior in heat resistance, and has excellent adhesion to the substrate. It has been found that it has the above
• the present invention has been completed based on the findings as described above.
• the acid (C) and the ketone As the solvent (D) coexists, as is clear from the results shown in Test Example 1 below, during storage, the epoxy resin ( ⁇ ) contained in the composition is partially acid (C) and ketone-based. It reacts with the solvent (D) to form a 1,3-dioxolane ring, and an epoxy resin having a structure in which a part of the epoxy group of the epoxy resin ( ⁇ ) has a 1,3-dioxolane ring.
• the composition Since this 1,3-dioxolane ring inhibits the reaction with carboxylic acid, the composition has excellent storage stability without gelling during storage. That is, since the 1,3-dioxolane ring is partially formed in the epoxy resin, the reactivity between the formed epoxy resin having the 1,3-dioxolane ring and the carboxyl group-containing compound is 1,3_dioxolane ring. Decreases by the presence of. Therefore, even when an epoxy resin having a 1,3-dioxolanic ring and a compound containing a carboxynole group coexist in the composition, the storage stability is excellent.
• the 1,3-dioxolane ring is partially formed on 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 carboxynole group-containing compound is not the same as the original (ordinary) epoxy resin and carboxylic acid. It is not inferior to a cured coating film obtained by reaction with a sil group-containing compound, and has excellent properties as described above.
• an epoxy resin (B_2) having a 1,3-dioxolane ring obtained by partially adding a ketone to a polyfunctional epoxy resin is, for example, a reaction rate S of keton to an epoxy resin, epoxy group 1
• the carbonyl group is 0.03 to 0.9 equivalent with respect to the equivalent, it has a structure having an unreacted epoxy group and a 1,3-dioxolane ring formed by the reaction of the epoxy group and the ketone.
• the cured film obtained by the reaction of an epoxy resin having a 1,3-dioxolane ring and a carboxyl group-containing compound is the original (normal) It is not inferior to a cured coating film obtained by the reaction of a functional epoxy resin and a carboxyl group-containing compound, and has excellent properties as described above.
• an epoxy resin ( ⁇ -2) having a 1,3-dioxolane ring the storage stability of the resulting curable composition is higher than that of using a normal polyfunctional epoxy resin.
• an epoxy resin having a 1,3-dioxolanic ring still has a sufficient amount of epoxy groups, so that when it is stored at room temperature for a long period of time, it reacts with a compound containing a carboxyleno group. There is a tendency to gel.
• the present inventors have found that the curability containing each of the components as described above.
• the acid (B) and the ketone solvent (C) By adding the acid (B) and the ketone solvent (C) to the composition, the reaction between the epoxy resin and the carboxyl group-containing compound is further suppressed, and better storage stability is obtained over a long period of time. I found that I can do it.
• liquid curable composition if it is stored in a container in a sealed state, it will not gel during long-term storage for more than half a year at room temperature.
• a dry film for example, by storing it in a vacuum pack, it does not gel even if stored for a long period of time of half a year or more at room temperature.
• the curable composition of the present invention to be contained is excellent in storage stability, can be composed in a one-pack type, and exhibits excellent alkali developability, photocurability and Z or thermosetting, By selectively exposing, developing and finishing curing the coating, a cured product excellent in crack resistance, electrical insulation, PCT resistance, adhesion, solder heat resistance, chemical resistance, electroless gold adhesion resistance, etc. Obtainable.
• the curable composition of the present invention will be described in detail.
• the carboxyl group-containing compound (A) and the carboxyl group-containing photosensitive compound ( ⁇ ′), which are one component of the present invention are compounds having at least one, preferably two or more carboxy groups in one molecule. (In the present specification, these may be collectively referred to as a carboxyl group-containing compound).
• a carboxyl group-containing compound Specifically, the les themselves that do not have an ethylenically unsaturated double bond, a carboxyl group-containing compound ( ⁇ ) and a carboxyl group-containing photosensitive compound ( ⁇ ⁇ ⁇ ⁇ ′) having an ethylenically unsaturated double bond. Any of them can be used and is not limited to a specific one, but particularly the compounds listed below (either oligomers or polymers) can be preferably used.
• the carboxyl group-containing photosensitive compound ( ⁇ '-1) is obtained by adding an unsaturated group-containing monocarboxylic acid (b) or an unsaturated group-containing compound (a) having two or more epoxy groups in one molecule.
• a reaction product (e) obtained by reacting a mixture (d) of a saturated carboxyl group-containing monocarboxylic acid (b) with a compound (c) having a reactive group that reacts with an epoxy group is further added to a polybasic acid anhydride ( The reaction is obtained by reacting f), and each reaction is easily performed in a solvent using a catalyst as described later.
• Examples of the compound (a) having two or more epoxy groups in one molecule include, for example, Epicoat 828, Epicote 834 manufactured by Japan Epoxy Resin Co., Ltd. Epicote 1001, Epicote 1004, Dainippon Ink & Chemicals Co., Ltd. Epiclon 840, Epiclon 850, Epiclon 1050, Epiclon 2055, Toto Kasei Co., Ltd. Potato YD-011, YD-013, YD-127, YD-128, D.E.R.
• Epoxy Coat manufactured by Japan Epoxy Shirazin 807 Bisphenol F type epoxy resin such as YDF-170, YDF-175, YDF-2004 (all trade names) manufactured by Toto Kasei Co., Ltd .; , ST-2007, ST-3000 (both trade names) and other hydrogenated bisphenolate type A epoxy resins; Japan Epoxy Resin Co., Ltd. Epicoat 604, Toto Kasei Co., Ltd. Epototo YH-434, Sumitomo Chemical Gumi such as Sumie Epoxy ELM-120 (all are trade names) manufactured by Kogyo Co., Ltd.
• Cydylamine type epoxy resin Alicyclic epoxy resin such as Celoxide 2021 (trade name) manufactured by Daicel Chemical Industries, Ltd .; YL_933 manufactured by Japan Epoxy Resin Co., Ltd. EPPN_501, EPPN manufactured by Nippon Kayaku Co., Ltd. — 502 (all trade names) and other trihydroxyphenylmethane type epoxy resins; Japan Epoxy Resin Co., Ltd.
• Y L-6056, YX-4000, YL— 6121 (all trade names) and other bixylenol types Or biphenol type epoxy resin or their mixture; EBPS-200 manufactured by Nippon Kayaku Co., Ltd., EPX-30 manufactured by Asahi Denka Kogyo Co., Ltd., EXA_ 1514 manufactured by Dainippon Ink & Chemicals Co., Ltd. Bisphenol S-type epoxy resin such as name); Epoxy Coat 157S (trade name) manufactured by Japan Epoxy Resin Co., Ltd .; Epoxy resin Yep — manufactured by Epoxy Resin Co., Ltd.
• Tetrafluoroethane type epoxy resin such as 931 (trade name); heterocyclic epoxy resin such as TEPIC (trade name) manufactured by Nissan Chemical Co., Ltd .; manufactured by NOF Corporation Diglycidyl phthalate resin such as DGT (trade name); Tetraglycidino lexylenoyl ⁇ tan resin such as ZX-1063 (trade name) manufactured by Toto Kasei Co., Ltd .; manufactured by Nippon Steel Chemical Co., Ltd.
• Naphthalene group-containing epoxy resins such as ESN-190, ESN-360, HP-4032, EXA-4750, EXA-4700 (all trade names) manufactured by Dainippon Ink and Chemicals, Inc .; Epoxy resins having a dicyclopentagen skeleton such as HP-7200 and HP-7200H (both trade names) manufactured by Co., Ltd .; CP_50S and CP-50M (both trade names manufactured by NOF Corporation) ) Glycidyl meta acrylate copolymer epoxy resin; and hydantoin Epoxy resin, co-polymerized epoxy resin of cyclohexenoremaleimide and glycidyl methacrylate, 1,5-dihydroxynaphthalene and bisphenol A-type epoxy resin obtained by reacting with epoxy type secondary hydroxyl group Forces including, for example, polyfunctional epoxy resins obtained by reacting hydrin (International Publication WO 01/024774) are not limited thereto. These epoxy resins can be used alone or in
• unsaturated group-containing monocarboxylic acid (b) include acrylic acid, metathallic acid, crotonic acid, cinnamic acid, ⁇ -cyananocinnamic acid, ⁇ -styrylacrylic acid, ⁇ -furfurylacrylic acid. Etc. Of these, acrylic acid and / or methacrylic acid are preferred because of their effects on photoreactivity and physical properties of the cured product, particularly heat resistance, electrical properties, and moisture absorption resistance. These unsaturated group-containing monocarboxylic acids can be used alone or in admixture of two or more.
• Representative examples of the compound (c) having a reactive group that reacts with the epoxy group include polyhydroxy such as dimethylolpropionic acid, dimethylolacetic acid, dimethylolbutyric acid, dimethylolvaleric acid, and dimethylolcaproic acid.
• dialkanolamines such as diethanolamine and diisopropanolamine
• dialkanolamines such as diethanolamine and diisopropanolamine
• 2, 6— Hydroxyalkyl phenols or hydroxyalkyl cresols such as dimethyl-4-hydroxymethylphenol, 2,4-dihydroxymethyl-2-cyclohexylphenol, trimethylolphenol, 3,5-dimethyl-2,4,6-trihydroxymethylphenol
• a phenol having a carboxyl group-containing substituent such as hydroxybenzoic acid, hydroxyphenylbenzoic acid, or hydroxyphenoxybenzoic acid,
• the reaction with the mixture (d) is usually carried out at about 50 to 150 ° C. in the presence of a polymerization inhibitor such as hydroquinone or oxygen in the presence of an organic solvent described later.
• a tertiary amine such as triethylamine, a quaternary ammonium salt such as triethylbenzylammonium chloride, an imidazole compound such as 2-ethyl-4-methylimidazole, or a phosphorus compound such as triphenylphosphine. Etc. may be added as a catalyst.
• the reactant (e) is further reacted with a polybasic acid anhydride (f) to obtain a carboxylate group-containing photosensitive compound ( ⁇ '-1) used in the composition of the present invention.
• the amount of the polybasic acid anhydride (f) used is such that the acid value of the resulting carboxylate group-containing photosensitive compound is preferably 30 to 200 mgK0H / g, more preferably 30 to: The added amount is 150 mgK0H / g.
• the acid value of the carboxylate group-containing photosensitive compound is lower than 30 mg KOH / g, the solubility in an alkaline aqueous solution is deteriorated, and the formed film is difficult to be visualized.
• it is higher than 200 mgKOHZg the surface of the exposed portion is developed regardless of the exposure conditions, which is not preferable.
• the above reaction is usually carried out at about 50 to 150 ° C in the presence of a polymerization inhibitor such as hydroquinone or oxygen in the presence of an organic solvent described later.
• a polymerization inhibitor such as hydroquinone or oxygen in the presence of an organic solvent described later.
• a tertiary amine such as triethylamine
• a quaternary ammonium salt such as triethylbenzyl ammonium chloride
• an imidazole compound such as 2-ethyl-4-methylimidazole
• triphenylphosphine etc.
• the polybasic acid anhydride (f) includes methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, nadic anhydride, 3, 6_endomethylenetetrahydro Aliphatic dibasic acid anhydrides such as phthalic anhydride, methylendomethylenetetrahydrohydrophthalic acid, tetrabromophthalic anhydride; succinic anhydride, maleic anhydride, itaconic anhydride, otatur succinic anhydride, pentadodecenyl succinic anhydride , Phthalic anhydride, trimellitic anhydride, or other aliphatic or aromatic dibasic acid anhydrides; or biphenyltetracarboxylic dianhydride, diphenylethertetracarboxylic dianhydride, butanetetracarboxy
• the carboxyl group-containing photosensitive resin () '-2) is a compound having three or more phenolic hydroxyl groups in one molecule (hereinafter referred to as a polyfunctional phenolic hydroxyl group-containing compound) ( g), particularly a reaction product (j) obtained by reacting a novolac-type phenol resin (g ′) with an alkylene oxide (h) and / or a cyclic carbonate (i), It can be obtained by reacting b) and then reacting the resulting reaction product (k) with polybasic acid anhydride (f). Each reaction can be easily carried out in a solvent using a catalyst as described below. To be done.
• Examples of the polyfunctional phenolic hydroxyl group-containing compound (g) include novolak-type phenol resins, condensates of phenols with aromatic aldehydes having phenolic hydroxyl groups, poly-p-hydroxystyrene, 1_naphthol or 2_ Condensates such as naphthol and aldehydes (ie, naphthol type novolak resins), 1, 2_, 1, 3_, 1, 4_, 1, 5_, 1, 6_, 2, 3_, 2, 6 or 2, 7-dihydroxy Condensates of naphthalene and aldehydes, condensates of mononaphthol and the above-mentioned dihydroxynaphthalene and aldehydes, condensates of mono or dihydroxy naphthalene and xylylene glycols, adducts of mono or dihydroxynaphthalene and gen compounds, etc.
• novolak-type phenol resins condensates of
• novolac type phenol resin (g ′) is preferable.
• Novolac type phenolic resin (g ') The force obtained by the condensation reaction of phenols with formaldehyde is usually carried out in the presence of an acidic catalyst.
• phenols include phenol, cresol, ethyl phenol, propyl phenol, butyl phenol, hexyl phenol, octyl phenol, nourphenol, phenol phenol, cuminophenol and the like.
• a functional group containing a halogen atom, oxygen, nitrogen, ion, etc. on a hydrocarbon skeleton bonded to a phenol ring or a phenol ring for example, Halogen group, ether group, ester group, carbonyl group, hydroxyl group, aldehyde group, amino group, amide group, nitrile group, nitro group, thiol group, thioether group, and other heteroaromatic groups such as pyridinole group and imidazole group Including those having
• the addition ratio of alkylene oxide (h) and / or cyclic carbonate (i) to the polyfunctional phenolic hydroxyl group-containing compound (g) is the same as the phenolic hydroxyl group of the polyfunctional phenolic hydroxyl group-containing compound (g). Per equivalent, it is preferably from 0 ⁇ 3 to: 10.0 monole, more preferably from 1.0 to 6.0 monole. In the case of less than 0.3 monole and more than 10.0 monole, the photocurable property of the resulting canoleboxyl group-containing photosensitive compound ( ⁇ ′-2) may be poor.
• the addition ratio of alkylene oxide (h) and / or cyclic carbonate (i) to nopolac-type phenol resin (g ′) is 0. 0 per equivalent of phenolic hydroxyl group of novolac-type phenol resin (g ′). 3 ⁇ 5.0 Monoreka S-preferred. If 0.3 below Monore and more 5.0 Monore multi Rere force Rupokishiru group-containing photosensitive compound ( ⁇ '- 2) it is a fear force s photocurable and developability becomes poor in.
• the addition reaction of the alkylene oxide (h) and / or the cyclic carbonate (i) to the polyfunctional phenolic hydroxyl group-containing compound (g) includes, for example, alkali metal compounds such as sodium hydroxide and potassium hydroxide; Quaternary basic salt compounds such as benzylammonium hydride mouth oxide, tetramethylammonium hydride mouth oxide, tetraethylammonium hydride mouth oxide, or the like; or a mixture of an alkali metal compound and a quaternary basic salt compound; Alternatively, a phosphorus compound such as triphenylphosphine is used as a catalyst, for example, ethylene glycol-monoremino ethinoreate acetate, ethylene glycol enobutenoreate ester acetate, diethylene glycol enomonoethylateate acetate, diethylene glycol Acetate monobutyl ether acetate, propylene glycol mono
• alkylene oxide (h) examples include ethylene oxide, propylene oxide, butylene oxide, trimethylene oxide, tetrahydrofuran, and tetrahydropyran.
• Examples of the cyclic carbonate (i) include ethylene carbonate, propylene carbonate, butylene carbonate, and 2,3-carbonate propyl methacrylate.
• ethylene carbonate, propylene carbonate, butylene carbonate, and 2,3-carbonate propyl methacrylate Preferably, 5-membered ethylene carbonate and propylene carbonate react with each other.
• the power and supply system are favorable.
• These cyclic carbonates can be used alone or in combination of two or more.
• the reaction temperature in the esterification reaction is preferably about 50 to 150 ° C.
• the reaction can be carried out under reduced pressure, normal pressure, or calo pressure.
• reaction solvent examples include n-hexane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, trichloroethane, tetrachloroethylene, methylchloroform, diisopropyl ether, ethylene glycol monoethyl ether acetate, and ethylene.
• Acetic esters such as glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, and aromatics such as toluene, xylene, tetramethylbenzene Group hydrocarbons are preferably used. These solvents can be used alone or in admixture of two or more.
• esterification catalyst sulfuric acid, hydrochloric acid, phosphoric acid, boron fluoride, methanesulfonic acid, benzenesulfonic acid, P-toluenesulfonic acid, cation exchange resin, and the like are appropriately used.
• the esterification reaction is preferably carried out in the presence of a polymerization inhibitor.
• Polymerization inhibitors include hydroquinone, methylenohydroquinone, hydroquinone monomethyl ether, catechol, pyrogallol, etc. Preferably used.
• the reaction product (k) of the reaction product (j) and the unsaturated group-containing monocarboxylic acid (b) is reacted with a polybasic acid anhydride (f) to produce a carboxyl group-containing photosensitive compound (
• the amount of the polybasic acid anhydride (f) used is such that the acid value of the resulting carboxyl group-containing photosensitive compound ( ⁇ '-2) is preferably 30 to 150mgKOHZg, more preferably 30-120111 ⁇ 1 ⁇ ⁇ 1 ⁇ / ⁇ Addition amount that will be ⁇ 1 ⁇ ⁇ 1 ⁇ / ⁇ .
• the above reaction is usually carried out in the presence of a polymerization inhibitor such as hydroquinone or oxygen in the presence of an organic solvent described later, usually at about 50 to 150 ° C.
• a polymerization inhibitor such as hydroquinone or oxygen in the presence of an organic solvent described later, usually at about 50 to 150 ° C.
• a tertiary amine such as triethylamine, a quaternary ammonium salt such as triethylbenzylammonium chloride, an imidazole compound such as 2-ethyl-4-methylimidazole, or a phosphorus compound such as triphenylphosphine is used as a catalyst. It may be added.
• the carboxyl group-containing photosensitive compound ( ⁇ '-2) is a polyfunctional phenolic hydroxyl group-containing compound (g), in particular, an alkylene oxide (h) and / or a cyclic carbonate of a novolac-type phenol resin (g '). It is excellent in flexibility and elongation due to chain extension by addition reaction of (i), and addition of unsaturated monocarboxylic acid (b) to the terminal hydroxyl group generated by addition reaction of alkylene oxide and polybasic acid anhydride (f ) Is added, and there is no unsaturated group or carboxyl group on the same side chain, and each is located at the end of the side chain. Excellent alkali developability due to presence of group.
• the blending ratio may be arbitrary depending on the purpose. ,Power It is preferable to mix the carboxyl group-containing photosensitive compound ( ⁇ ′-2) in the ratio of 80:20 to 20:80 with respect to the lupoxyl group-containing photosensitive compound ( ⁇ ′-1).
• carboxyl group-containing compounds ( ⁇ ⁇ ) and carboxyl group-containing photosensitive compounds (′) that can be suitably used in the present invention include the following compounds (oligomers and polymers: ).
• a copolymer of an acid anhydride (o) having an unsaturated double bond and a compound (m) having an unsaturated double bond is reacted with a compound (P) having a hydroxyl group and an unsaturated double bond.
• the epoxy group of the copolymer (m) and glycidinole (meth) acrylate with an unsaturated double bond has one carboxyl group per molecule and no ethylenically unsaturated bond.
• a carboxylate group-containing compound obtained by reacting an organic acid (q) and reacting the resulting secondary hydroxyl group with a saturated or unsaturated polybasic acid anhydride (f),
• a compound (n) having an epoxy group and an unsaturated double bond is added to a carboxyl group-containing compound obtained by reacting a hydroxyl group-containing polymer (r) with a saturated or unsaturated polybasic acid anhydride (f).
• An unsaturated group-containing polycarboxylic acid urethane compound comprising a reaction product with the nate (t),
• a polyfunctional oxetane compound (u) having at least two oxetane rings in one molecule is reacted with an unsaturated monocarboxylic acid (b), and saturated with respect to the primary hydroxyl group in the resulting modified oxetane compound.
• the carboxyl group-containing compound (1) is an unsaturated carboxylic acid such as (meth) acrylic acid.
• (1) is a copolymer of a compound (m) having an unsaturated double bond such as styrene, ⁇ -methylstyrene, lower alkyl (meth) acrylate, isobutylene, etc.
• the group-containing photosensitive compound has a butyl group, a aryl group, a (meth) alkyl group in a part of the carboxyl group of the copolymer of the unsaturated carboxylic acid (1) and the compound (m) having an unsaturated double bond.
• the carboxyl group-containing photosensitive compound (3) is a compound (n) having an epoxy group and an unsaturated double bond in the molecule, such as glycidyl (meth) acrylate, a-methyl daricidyl (meth) acrylate.
• the carboxyl group of the unsaturated carboxylic acid (1) is reacted with the epoxy group of the copolymer of the compound (m) having an unsaturated double bond with
• a polybasic acid anhydride (f) such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydroanhydride is added to the secondary hydroxyl group formed by the above addition reaction. It is a compound in which a carboxynole group is introduced into the side chain by reacting phthalic acid or the like with an esterich reaction.
• the carboxyl group-containing photosensitive compound (4) has an acid anhydride (o) having an unsaturated double bond, such as maleic anhydride, itaconic anhydride, and the like, and the unsaturated double bond.
• a hydroxyl group such as a monomer obtained by reacting force with prolatatone and a macromonomer obtained by reacting (meth) acrylate with a poly force prolatatone oligomer is converted into a half ester, and the unsaturated double bond of the compound (p) is formed. It is a compound introduced into the side chain.
• the carboxyl group-containing compound (5) is a compound such as an alkyl (meth) acrylate having a unsaturated double bond and no hydroxyl group or acidic group, substituted or unsubstituted styrene (m ) And an organic acid (q) having one carboxynole group in one molecule and no ethylenically unsaturated bond in the glycidyl group of a copolymer having glycidyl (meth) atarylate as the main chain, for example, A compound obtained by reacting an alkyl carboxylic acid having 2 to 17 carbon atoms, an aromatic group-containing alkyl carboxylic acid, or the like, and adding the polybasic acid anhydride (f) to the resulting secondary hydroxyl group.
• the carboxylate group-containing compound (6) is a hydroxyl group-containing polymer (r), such as an olefinic hydroxyl group-containing polymer, an acrylic polyol, a rubber polyol, a polyvinyl acetal, a styrene aryl alcohol resin, or a cellulose.
• Etc. a compound having a carboxylate group introduced by reacting the polybasic acid anhydride (f 1) having a relatively weak acidity.
• the carboxyl group-containing photosensitive compound (7) the carboxyl group of the carboxyl group-containing compound (6) is reacted with the epoxy group of the compound (n) having an unsaturated double bond with the epoxy group.
• a compound in which an unsaturated double bond of the compound (n) is introduced into the side chain.
• compound (s) having at least two or more hydroxyl groups in one molecule and one other reactive group other than a hydroxyl group that reacts with an epoxy group for example, carboxyl group, secondary amino group, etc.
• an epoxy group for example, carboxyl group, secondary amino group, etc.
• examples thereof include polyhydroxy-containing monocarboxylic acids such as dimethylolpropionic acid, dimethylolacetic acid, dimethylolbutyric acid, dimethylolvaleric acid, and dimethylolcaproic acid; and dialial amines such as diethanolamine and diisopropanolamine. Is mentioned.
• reaction product (I) polybasic acid anhydride (f)
• the synthesis reaction involves reacting the reaction product (I) with the polybasic acid anhydride (f). Then, it is preferable to react the unsaturated group-containing monoisocyanate (t) with the hydroxyl group in the produced unsaturated group-containing polycarboxylic acid compound.
• unsaturated group-containing monoisocyanate (t) include, for example, metatalloy leuocyanate, methacryloyloxychetyl isocyanate, organic diisocyanate (for example, tolylene diisocyanate, xylylene diisocyanate, Reaction products obtained by reacting isophorone diisocyanate, hexamethylene diisocyanate, etc.) with (meth) atarylates having one hydroxyl group in one molecule at an equimolar ratio, etc.
• organic diisocyanate for example, tolylene diisocyanate, xylylene diisocyanate, Reaction products obtained by reacting isophorone diisocyanate, hexamethylene diisocyanate, etc.
• the carboxyl group-containing photosensitive compound (9) is obtained by using a compound having an oxetane ring as a starting material in place of an epoxy resin that mainly generates a secondary hydroxyl group by reaction with an unsaturated monocarboxylic acid.
• the polyfunctional oxetane compound (u) is reacted with an unsaturated monocarboxylic acid), and the primary hydroxyl group of the resulting modified oxetane compound is further reacted with a polybasic acid anhydride ⁇ to form a binding site. Is a compound with excellent thermal stability that is difficult to be thermally cut.
• the carboxyl group-containing photosensitive compound of the above (10) and (11) is a bisphenol ⁇ type Epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, brominated bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, biphenol type epoxy resin, bixylenol type epoxy resin, etc.
• unsaturated double bonds are introduced by reacting ethylenically unsaturated groups such as bur, allyl, and (meth) atalyloyl groups with hydroxyl groups remaining in the above reaction, carboxynole groups, etc., and hydroxyl groups formed. It is carried out by reacting a compound having a reactive group such as an epoxy group having acid and an acid chloride.
• the acid value of the carboxyl group-containing compound (A) and the carboxyl group-containing photosensitive compound (A,) as described above is preferably 20 to 200 mg KOH / g, more preferably 50 to 120 mg KOH / g.
• the acid value is lower than 20 mgKOH / g, the solubility in an aqueous alkali solution is deteriorated, and development of the formed coating film becomes difficult.
• 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 (A) and the carboxyl group-containing photosensitive compound ( ⁇ ′) as described above can be used alone or in combination of two or more.
• an epoxy resin ( ⁇ ⁇ ⁇ ⁇ )
• a ketone is partially added to a multifunctional epoxy resin ( ⁇ _1) having two or more epoxy groups in one molecule and a polyfunctional epoxy resin.
• the resulting epoxy resin ( ⁇ -2) having a 1,3-dioxolane ring can be used alone or in combination of two or more.
• These epoxy resins improve the properties such as adhesion and heat resistance of the resist to various substrates by thermosetting.
• the compounding amount is 100 parts by mass (total amount) of the carboxyl group-containing compound ( ⁇ and / or A ′).
• the ratio of 5 parts by mass or more, preferably 10 parts by mass or more and 100 parts by mass or less is sufficient with respect to the single amount; The ratio of parts. If the blending amount of the epoxy resin (B) is less than the above range, the cured film becomes highly hygroscopic and the PCT resistance tends to decrease, and the solder heat resistance and electroless plating resistance tend to decrease. On the other hand, if the above range is exceeded, the developability of the coating film and the resistance to electrical square plating of the cured film will be poor, and the PCTl film will be poor.
• Examples of the polyfunctional epoxy resin (B_l) include the epoxy resins exemplified as the polyfunctional epoxy compound (a) having two or more epoxy groups in one molecule.
• the polyfunctional epoxy compound (a) having two or more epoxy groups in one molecule For electronic materials, polyfunctional epoxy resins having 3 or more epoxy groups in one molecule are preferred, and among these, novolak type epoxy resins are particularly preferred from the viewpoint of physical properties of the cured product.
• the epoxy resin having a 1,3-dioxolane ring ( ⁇ _2) can be easily obtained by partially adding a polyfunctional epoxy resin and a ketone using an acid as a catalyst.
• the reaction rate of the ketone with respect to the polyfunctional epoxy resin is such that the power of the phenolic base is SO.
• 03-0.9 equivalent to 1 equivalent of the epoxy group preferably 0.05-0.8 equivalent, more preferably Is 0.:! To 0.7 equivalents, particularly preferably 0.2 to 0.5 equivalents.
• polyfunctional epoxy resin examples include the epoxy resins exemplified as the polyfunctional epoxy compound ( a ) having two or more epoxy groups in one molecule.
• polyfunctional epoxy resins having 3 or more epoxy groups in one molecule are preferred, and among these, novolak epoxy resins are particularly preferred from the viewpoint of reactivity.
• Examples of the ketone include acetone, methyl ethyl ketone, methyl n-propyl ketone, methyl isobutyl ketone, methyl _n-butyl ketone, methylolene n-aminoleketone, ethenyl benzeno ketone, di-n-amyl ketone, n-hexyl benzyl ketone, cyclohexane.
• Examples include hexanone, acetophenone, and benzoin.
• Examples of the acid used as a catalyst for the reaction include phosphoric acid, hydrochloric acid, sulfuric acid, phosphotungstic acid, boron trifluoride ether complex, key tungstic acid, trifluoromethanesulfonic acid, triphosphoric acid, trimetaphosphoric acid, tetrametalin.
• Acid phosphates such as polyphosphoric acid such as acid, methyl acid phosphate, isodecyl acid phosphate and oleyl acid phosphate
• inorganic acids and boron trifluoride ether complexes are preferred from the viewpoint of yield, and phosphoric acid and acidic phosphate ester, especially phosphoric acid are preferred from the viewpoint of electronic materials. 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 0.0:! To 5% by mass, particularly preferably 0. 0:! To 3% by mass. If the acid ratio exceeds 20% by mass, gelation may occur. On the other hand, if it is less than 0.001% by mass, a long time is required for the reaction between the polyfunctional epoxy resin and the ketone.
• the reaction of the polyfunctional epoxy resin and the ketone is preferably performed in the ketone, but a ketone and another solvent, for example, a mixed solvent of ketone and toluene, or a mixed solvent of ketone and carbitol is used. Can do.
• the reaction temperature is preferably 0 to 100 ° C, more preferably 10 to 80 ° C. If the reaction temperature exceeds 100 ° C, gelation may occur. On the other hand, if the reaction temperature is less than o ° c, the reactivity decreases, which is not preferable.
• the acid (C) and the ketone solvent (D) are mainly used as a storage stabilizer as described above.
• the acid (C) the ability to use an inorganic acid, an organic acid, an acidic phosphate ester, or the like similar to the acid catalyst used when the ketone is partially added to the epoxy resin.
• phosphoric acid and acidic phosphoric acid esters 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 epoxy resin (B), more preferably 0.01 to 10% by mass, particularly preferably 0.0% by mass. :! ⁇ 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, it is difficult to obtain the effect of storage stability.
• ketone solvent (D) various ketones used in the partial addition reaction of the ketone with the epoxy resin can be used alone or as a mixture of two or more.
• the blending amount is suitably 5 parts by mass or more with respect to 100 parts by mass of the epoxy resin (B).
• the upper limit of the amount of the ketone solvent (D) is not particularly limited and can be appropriately set according to the desired viscosity of the curable composition.
• Examples of the photosensitive (meth) atalytoy compound (E) include 2-hydroxyethyl (meth) ) Hydroxyl-containing acrylates such as acrylate, 2-hydroxypropyl (meth) acrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, water such as polyethylene glycol diatalate, polypropylene glycol diatalate Soluble Atarylates; Multifunctional Polyester Atallates of Polyhydric Alcohols such as Trimethylolpropane Tri (meth) atalylate, Pentaerythritol Tetraatalylate, Dipentaerythritol Hexaatalylate; Trimethylolpropane, Hydrogenated Polyfunctional alcohols such as bisphenol A or polyphenols such as bisphenol A and biphenols and / or propylene oxide adducts Polyfunctional or monofunctional polyurethane urethane acrylate which is an isocyanate modification of
• Some epoxy atalylates such as force prolatatone-modified ditrimethylolpropane tetraatalylate, ⁇ -force prolactron-modified dipentaerythritol acrylate, force prolataton-modified hydroxybivalic acid neopentyl glycol ester diatalylate
• atalylates such as force prolatatone-modified ditrimethylolpropane tetraatalylate, ⁇ -force prolactron-modified dipentaerythritol acrylate, force prolataton-modified hydroxybivalic acid neopentyl glycol ester diatalylate
• attalelates and metatalates corresponding to the above-mentioned atarylates and these can be used alone or in combination
• a polyfunctional (meth) ataryl one-toy compound having two or more (meth) atalyloyl groups in one molecule is preferable.
• the purpose of use of these photosensitive (meth) attalei toy compounds is to make the composition photocurable.
• the photosensitive (meth) acrylate compound that is liquid at room temperature adjusts the composition to a viscosity suitable for various coating methods, and helps solubility in aqueous alkali solutions. Also plays a role.
• the dryness of the coating film cannot be obtained and the characteristics of the coating film tend to deteriorate.
• the amount of the photosensitive (meth) acrylate compound ( ⁇ ) is preferably 100 parts by mass or less with respect to 100 parts by mass of the carboxyl group-containing compound ( ⁇ ).
• a photosensitive (meth) acrylate compound ( ⁇ ) can be blended with the carboxyl group-containing photosensitive compound ( ⁇ ) for the purpose of increasing photoreactivity.
• the amount of the photosensitive (meth) ataretoy compound ( ⁇ ) is 100 parts by mass with respect to 100 parts by mass of the carboxylate group-containing photosensitive compound ( ⁇ ′). Part or less is preferred.
• the term “(meth) atalylate” is a term that collectively refers to attalylate and metatalariate, and the same applies to other similar expressions.
• Examples of the photopolymerization initiator (F) include benzoin and benzoin alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether; acetophenone, 2,2-dimethoxy-1,2-phenacetopheno , 2,2-diethoxy-1-2-phenylacetophenone, 1,1-dichloroacetophenone and other acetophenones; 2-methyl-1- 1- [4- (methylthio) phenyl] _2-morpholinopropanone 1 _one, 2-benzyl-2-dimethylamino 1 _ (4 morpholinophenyl) 1 butane _ 1 _1, aminoacetophenones such as N, N-dimethylenoreaminoacetophenone; 2 —methylanthraquinone , 2-Ethylanthraquinone, 2 _t-butylanthraquinone, 1_
• photopolymerization initiators can be used alone or as a mixture of two or more thereof. Further, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, pentyl-1-dimethylaminobenzoate, Photoinitiator aids such as tertiary amines such as trichinoleamine and triethanolamine can be provided. In addition, a titanocene compound such as CGI-784 having an absorption in the visible light region (manufactured by Ciba Specialty Chemicals Co., Ltd.) can also be added to promote the photoreaction.
• CGI-784 having an absorption in the visible light region
• photopolymerization initiators are 2, 4, 6_trimethylbenzoyldiphenylphosphine oxide, 2-methyl-1_ [4_ (methylthio) phenyl] _2_morpholinopropane_1_one, 2_ Be Nyl 2-dimethylamino 1- (4-morpholinophenyl) 1-butane 1-one, etc.
• it is not limited to the above, but absorbs light in the ultraviolet or visible light region, and (meth) atalyloyl group
• unsaturated groups such as photopolymerization initiators and photoinitiators, they can be used alone or in combination.
• the amount used is from 0.5 to 100 parts by weight (total amount or single amount in the case of single use) of the carboxyl group-containing compound (A) and / or the carboxyl group-containing photosensitive compound ( ⁇ ′). A proportion of 25 parts by weight is preferred.
• the curable composition of the present invention includes a carboxyl group-containing compound ( ⁇ ⁇ ) or a carboxyl group-containing photosensitive compound ( ⁇ ′), an epoxy resin ( ⁇ ), a photosensitive (meth) attalito toy compound ( ⁇ ⁇ ) or a carboxyl group-containing photosensitive compound ( ⁇ ′), an epoxy resin ( ⁇ ), a photosensitive (meth) attalito toy compound ( ⁇ ⁇ ) or a carboxyl group-containing photosensitive compound ( ⁇ ′), an epoxy resin ( ⁇ ), a photosensitive (meth) attalito toy compound (In order to dissolve (ii) and adjust the composition to a viscosity suitable for the coating method, an organic solvent other than the ketone solvent can be blended.
• organic solvent examples 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, Glycol ethers such as diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol jetyl ether, triethylene glycol monoethyl ether; ethyl acetate, butyl acetate, ethylene glycol Monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl Acetic esters such as ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether
• Aliphatic solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent-based naphtha. These organic solvents can be used alone or as a mixture of two or more.
• the amount of the organic solvent blended can be any amount depending on the application S, in general, the total amount of the carboxyl group-containing compound (A and / or ⁇ ′) and epoxy resin (B) 100 mass 30 to 1000 parts by mass
• the range of the degree is appropriate and can be appropriately set according to the coating method to be selected.
• the curable composition of the present invention can be blended with a curing catalyst to such an extent that the storage stability is not impaired.
• a curing catalyst include imidazole, 2-methylimidazole, 2-ethylimidazole, 2_ethyl_4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanethyl-2-phenylamine.
• 1_ (2-Cyanethyl) _2_Ethyl_4-Imidazole derivatives such as methylimidazole; Dicyandiamide, Benzyldimethylamine, 4_ (Dimethylamino) _N, N-Dimethylbenzylamine, 4-Methoxy-1-N, Use amine compounds such as N-dimethylbenzylamine, 4_methylmono-N, N-dimethylbenzylamine; hydrazine compounds such as adipic hydrazide and sebacic acid hydrazide; and phosphorus compounds such as triphenylphosphine. Is possible.
• Examples of commercially available products include 2MZ_A, 2MZ-OK, 2 ⁇ , 2 ⁇ 4 ⁇ , and 2 ⁇ 4 ⁇ (trade names of imidazole compounds) and S-PRO 3503N manufactured by Sanpro Corporation.
• U-CAT3502T all trade names of block isocyanate compounds of dimethylamine
• DBU dimethylamine
• DBN dimethylamine
• U-CATSA102 U-CAT 5002
• the catalyst is not limited to these, and any catalyst that cures a compound having a cyclic ether or a compound having a cyclic ether and a carboxylic acid may be used. Use alone or in combination of two or more will not work.
• the curing catalyst may be blended in an ordinary quantitative ratio.
• the carboxyl group-containing compound (A) and Z or carboxy group-containing photosensitive compound ( ⁇ ′) 100 parts by mass (total amount or single use) In this case, it is a ratio of 0.:! To 20 parts by mass, preferably 0.5-15.
• the curable composition of the present invention is an oxetane compound or the like for the purpose of improving characteristics.
• Compounds having other cyclic ethers can be blended.
• oxetane compound examples include 3, 7-bis (3-oxetanyl) -5-oxanonan, 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) methinole] propane, ethylene glycol bis (3_ethyl_3-oxetanylmethinole) ether, dicyclopenturbis (3_ethyl_3-oxetanyl Methinole) ether, triethylene glycol bis (3-ethynole _ 3-oxetanylmethino
• the curable composition of the present invention may further contain barium sulfate, barium titanate, amorphous silica, crystalline silica, fused silica, spherical silica, talc, clay, magnesium carbonate, carbonic acid, if necessary.
• inorganic fillers such as calcium, aluminum oxide, aluminum hydroxide and my strength can be used alone or in combination of two or more. These are used for the purpose of suppressing the curing shrinkage of the coating film and improving properties such as adhesion to various substrates and hardness.
• the compounding amount of the inorganic filler is 10 parts by mass with respect to 100 parts by mass (total amount or single amount in the case of single use) of the carboxyl group-containing compound (A) and / or the force oxyl group-containing photosensitive compound ( ⁇ ′).
• a proportion of ⁇ 300 parts by mass, preferably 30 to 200 parts by mass is appropriate.
• the curable composition of the present invention may further contain phthalocyanine blue, phthalocyanine green, iodin green, diazo yellow, crystal violet, Known conventional colorants such as titanium oxide, carbon black, naphthalene black, etc., known conventional thermal polymerization inhibitors such as hydride quinone, hydroquinone monomethyl ether, t-butylcatechol, pyrogallol, phenothiazine, fine silica, organic bentonite, montmorillo Known conventional thickeners such as lonite, defoamers and / or leveling agents such as silicones, fluorines and polymers, silane coupling agents such as imidazole, thiazole and triazole Known and commonly used additives can be blended.
• Known conventional colorants such as titanium oxide, carbon black, naphthalene black, etc.
• known conventional thermal polymerization inhibitors such as hydride quinone, hydroquinone monomethyl ether, t-butylcatechol
• binder resins such as copolymers of ethylenically unsaturated compounds such as acrylic acid esters, polyester resins synthesized from polyhydric alcohols and polybasic acid compounds, and polyesters
• Photopolymerizable oligomers such as (meth) acrylate, polyurethane (meth) acrylate, and epoxy (meth) acrylate can also be used as long as they do not affect the properties of the solder resist.
• the curable 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. it can .
• the compounding amount of the flame retardant is usually based on 100 parts by mass (total amount or single amount when used alone) of the carboxyl group-containing compound (A) and / or the carboxyl group-containing photosensitive compound ( ⁇ ′). 1 to 200 parts by mass, preferably 5 to 50 parts by mass.
• 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.
• water can be added to the curable composition of the present invention in order to reduce flammability.
• the carboxyl group of the carboxyl group-containing compound ( ⁇ ) and / or the carboxyl group-containing photosensitive compound ( ⁇ ′) is replaced with amines such as trimethylamine and triethylamine, ⁇ , ⁇ —
• the curable composition of the present invention is produced by salt formation with a (meth) acrylate resin having a tertiary amino group such as dimethylaminoethyl (meth) acrylate, ⁇ , ⁇ -dimethylaminopropyl (meth) acrylamide, attalyloyl morpholine, etc. It is preferable to adjust the object to water.
• the curable composition of the present invention may be in the form of a dry film comprising a support and a layer formed of the curable composition formed on the support.
• a peelable cover film is further laminated on the curable composition layer of the film.
• 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.
• the thickness of the support is appropriately selected within the range of 10 to 150 zm.
• the curable composition layer on the support is uniformly formed on the support by using a comma coater, a blade coater, a lip coater, a rod coater, a squeeze coater, a reno coat coater-a transfer coater coater, or the like. Power obtained by applying to thickness, heating and drying to volatilize solvent No particular limitation on thickness Thickness is appropriately selected in the range of 10 to 150 xm
• 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 force bar film is smaller than the adhesive force between the curable composition layer and the support.
• the curable composition of the present invention having the composition as described above is diluted as necessary to adjust the viscosity to be suitable for the coating method, and this is applied to, for example, a printed wiring board on which a circuit is formed. It is applied by printing, curtain coating, spray coating, roll coating, etc., and tack-free coating is performed by evaporating and drying the organic solvent contained in the composition at a temperature of about 60 to 100 ° C., for example. A film can be formed.
• a dry film comprising a support and a layer made of the curable composition formed on the support, it is bonded to a printed wiring board formed with a circuit using a hot roll laminator or the like (The curable composition layer and the printed wiring board on which the circuit is formed are bonded so that the coating film can be formed on the printed wiring board on which the circuit is formed.
• 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 formed with a circuit are in contact with each other.
• a hot roll laminator or the like can be used to form a coating film on a printed wiring board on which a circuit has been formed.
• a coating film is formed on a printed wiring board on which a circuit is formed (when the dry film is used, the support is not peeled off), and then an active energy ray such as a laser beam is directly applied according to the pattern.
• the resist pattern can be formed by exposing to an active energy line selectively through a photomask having a pattern or a pattern, and developing the unexposed portion with a dilute alkaline aqueous solution (when the above dry film is used, exposure is possible). Then, the support is peeled off and developed). After that, it can be electrically insulated 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.
• a cured film (cured product) with excellent PCT resistance, adhesion to various substrates, solder heat resistance, chemical resistance, and electroless gold adhesion resistance is formed.
• an alkaline aqueous solution of potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, amines or the like can be used.
• a low-pressure mercury lamp As the irradiation light source for photocuring, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a xenon lamp, a metal halide lamp, etc. are suitable.
• laser beams can be used as active energy rays.
• a novolak type talesol resin (trade name “Shonol C RG951”, phenolic hydroxyl group equivalent: 119) manufactured by Showa Polymer Co., Ltd. 4g / 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 the temperature was raised. Next ⁇ ⁇ ⁇ Prohi. Renren Xoxide, 63.8, was added dropwise and reacted at 125-132 ° C, 0-4.8 kg / cm 2 for 16 hours.
• each component was blended according to the formulation shown in Table 1 below and stirred to prepare each curable composition of Formulation Examples A and B. .
• Table 1 the formulation shown in Table 1 below and stirred to prepare each curable composition of Formulation Examples A and B.
• Each of the obtained curable compositions was placed in a container, sealed to prevent evaporation of acetone, and allowed to stand at room temperature and 50 ° C. for 7 days, respectively, and the relationship between the acid value and epoxy equivalent was examined. The results are shown in Table 2. In the case of Formulation Example B containing phosphoric acid, gelation did not occur even after standing at room temperature and 50 ° C for 7 days.
• the composition containing no phosphoric acid showed a decrease in acid value and an increase in epoxy equivalent when left at 50 ° C as compared to standing at room temperature. In other words, this means that the carboxylic acid and the epoxy resin reacted, thereby reducing the acid value and gelling.
• 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 13-dioxolane ring by acetone and phosphoric acid, and it did not gel because it inhibited the reaction between carboxylic acid and epoxy resin. it is conceivable that. Therefore, it can be seen from the results of the above Formulation Example B that a one-component solder resist ink can be prepared.
• the reaction is measured by oxidation and total oxidation of the reaction solution by potentiometric titration, followed by the rate of adhesion obtained, and the end point is a reaction rate of 95% or more.
• the carboxyl group-containing photosensitive resin thus obtained had a non-volatile content of 62% and a solid content acid value of 100 mgKH / g.
• the reaction product was cooled to 80 to 90 ° C., 106 parts of tetrahydrophthalic anhydride was added, reacted for 8 hours, cooled and taken out.
• the thus obtained carboxyl group-containing photosensitive compound had a nonvolatile content of 64% and a solid content acid value of 97 mgKOH / g.
• the cover film is peeled off, and the film is bonded to the surface-treated copper through-hole printed wiring board that has been patterned, and then a negative film having a resist pattern is adhered to the support side, and an ultraviolet exposure device ( Irradiate with ultraviolet rays (exposure amount 600mjZcm 2 ) using Oak Manufacturing Co., Ltd., model HMW-680GW, peel off the support, and 60 to 120 seconds with lwt% aqueous sodium carbonate solution. 2.
• Okg / cm 2 Development was performed at a spray pressure of 150 ° C, followed by heat curing for 60 minutes in a hot air dryer at 150 ° C to prepare a test substrate.
• test substrate having the obtained cured film With respect to the test substrate having the obtained cured film, the above-described test method and evaluation method were used for crack resistance, PCT resistance, adhesion, solder heat resistance, acid resistance, alkali resistance, and electroless gold adhesion resistance. Each test was conducted.
• test board was fabricated under the same conditions as above and tested for electrical insulation resistance. .
• Films of the compositions in Table 4 were stored at 20 ° C and evaluated according to the following criteria.
• the crack resistance of the cured film was evaluated using the Thermal Shock Chamber NT 1020W manufactured by Enomoto Kasei Co., Ltd., with one cycle of -65 150 ° C and the following criteria. However, only samples that did not gel (development time within 120 seconds) were tested.
• PCT resistance of the cured film was evaluated according to the following criteria under the conditions of 121 ° C, 100% humidity and 50 hours. However, only samples that did not gel (development time within 120 seconds) were tested.
• the cured film has no blistering, peeling or discoloration
• the cured film has some blistering, peeling or discoloration
• the cured film has blistering, peeling, or discoloration
• the cured film was cross-cut in a grid pattern, and then the peelability after the peeling test with the cellophane adhesive tape was visually judged. However, only samples that did not gel (development time within 120 seconds) were tested.
• JIS C 6481 the test substrate was immersed in a 260 ° C solder bath for 10 seconds three times to evaluate the change in appearance.
• post flux rosin type
• a flux according to C 6481 was used. However, the test was conducted only on the sample that did not gel (development time within 120 seconds).
• test substrate was immersed in a 10 vol% sulfuric acid aqueous solution at 20 ° C for 30 minutes and then taken out, and the state of the cured film was evaluated according to the following criteria. However, only samples that did not gel (development time within 120 seconds) were tested.
• 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, the test was carried out only on the gel and the sample (development time within 120 seconds).
• electroless gold plating was performed on the test substrate, the appearance of the test substrate was changed, and a peeling test using a cellophane adhesive tape was performed, and the peeled state of the cured film was determined according to the following criteria. . However, the test was carried out only for samples that did not gel (development time within 120 seconds).
• Degreasing The test substrate was immersed in a 30 ° C acidic degreasing solution (manufactured by Nippon McDermid Co., Ltd., 20 vol% aqueous solution of Metex L-5B) for 3 minutes.
• test substrate was immersed in an aqueous solution of 14.3 wt% ammonium persulfate for 3 minutes at room temperature.
• Acid immersion The test substrate was immersed in a 10 vol% sulfuric acid aqueous solution at room temperature for 1 minute.
• Catalyst application The test substrate was immersed for 7 minutes in a 30 ° C. catalyst solution (manufactured by Meltex Co., Ltd., 10 vol% aqueous solution of metal plate activator 350).
• Acid immersion The test substrate was immersed in a 10 vol% aqueous sulfuric acid solution at room temperature for 1 minute.
• washing with water The test substrate was immersed in running water for 30 seconds to 1 minute.
• test substrate was immersed in warm water of 60 ° C, washed thoroughly for 3 minutes, drained thoroughly, and dried.
• a test substrate having electroless gold plating was obtained through these steps.
• the electrical insulation of the cured film was evaluated according to the following criteria. However, only samples that did not gel (development time within 120 seconds) were tested.
• Humidification conditions Temperature 120 ° C, humidity 85% RH, applied voltage 30V, 50 hours. Measurement conditions: Measurement time 60 seconds, applied voltage 500V.
• a reaction vessel equipped with a stirrer, cooling tube, thermometer, and dropping funnel for continuous dripping is charged with 100 parts of nopolac type epoxy resin (Epototo YDCN-704 manufactured by Tohto Kasei Co., Ltd.) and 100 parts of acetone.
• the epoxy resin was dissolved in acetone by stirring at 20-25 ° C.
• a mixture of 1 part of 85% phosphoric acid and 50 parts of acetone is gradually added dropwise and reacted at 40-45 ° C for 24 hours to obtain a reactant solution having a nonvolatile content of 62% and a solid content epoxy equivalent of 223 g / eq. Got.
• the reaction ratio of the ketone to the epoxy resin was about 0.1 equivalent of carbonyl group to 1 equivalent of epoxy group.
• a reaction vessel equipped with a stirrer, a condenser, a thermometer, and a dropping funnel for continuous dripping is charged with 100 parts of a nopolac type epoxy resin (RE-306 manufactured by Nippon Kayaku Co., Ltd.) and 100 parts of acetone.
• the epoxy resin was dissolved in acetone by stirring at 20-25 ° C. Then slowly added dropwise to a mixture of 1 part acetone 50 parts of 85% phosphoric acid, allowed to react for 24 hours at 40 to 45 ° C, non-volatile components Hatsubun 62% solids epoxy equivalent 210g / e q. Of A reaction solution was obtained.
• the reaction ratio of keton to the epoxy resin was about 0.1 equivalent of carbonyl group to 1 equivalent of epoxy group.
• each component was blended according to the blending composition shown in Table 15, and stirred to prepare each curable composition.
• this curable composition is applied onto a support, dried by heating, a curable composition layer having a thickness of 20 30 zm is formed, a cover film is bonded, and the storage stability of the obtained film is determined. evaluated.
• test substrate was produced under the same operations and conditions as in the above Examples:! -7.
• the crack resistance, PCT resistance, adhesion, solder heat resistance, acid resistance, alkali resistance, and electroless gold plating resistance were tested and tested as described below. Each test of electrical insulation resistance was performed.
• Films of the compositions in Table 15 were stored at 5 ° C and evaluated according to the following criteria.
• Evaluation was performed in the same manner as in the test method of (2) crack resistance. However, only those with a development time of 180 seconds or less were tested.
• JIS C 6481 the test substrate was immersed once in a 260 ° C solder bath for 10 seconds, and the change in appearance was evaluated.
• post flux rosin type
• a flux according to C 6481 was used. However, the test was conducted only for the development time within 180 seconds.
• Evaluation was performed in the same manner as in the above (8) test method for resistance to electroless gold plating. However, the test was conducted only for the development time within 180 seconds.
• reaction solution was cooled to 60 ° C, charged with 13.8 parts of triphenylphosphine, heated to 100 ° C, reacted for about 32 hours, and reacted with an acid value of 0.5 mgKOH / g (hydroxyl group, 12 Equivalent).
• 364 ⁇ 7 parts (2.4 mol) of tetrahydrophthalic anhydride, 137 ⁇ 5 parts of diethylene glycol monoethyl ether acetate and 58.8 parts of solvent naphtha were added to this, and heated to 95 ° C for about 6 hours.
• the mixture was cooled to obtain a carboxyl group-containing photosensitive compound having a solid content acid value of 40 mgKH / g and a solid content concentration of 65%.
• the reaction product (hydroxyl group: 1.3 equivalents) is cooled to 80 to 90 ° C, and 91.2 parts (0.6 equivalents) of tetrahydrophthalic anhydride is added, reacted for 8 hours, and cooled. It was taken out later.
• the carboxyl group-containing photosensitive compound thus obtained had a nonvolatile content of 65% and a solid content acid value of 83 mgKOHZg.
• nopolac type epoxy resin (Epototo YDCN-704, manufactured by Tohto Kasei Co., Ltd.), novolak type epoxy resin ( 30 parts of RE-306) manufactured by Nippon Kayaku Co., Ltd. and 100 parts of acetone were charged and stirred at 20 to 25 ° C. to dissolve the epoxy resin in acetone. Then slowly added dropwise to a mixture of 1 part of 85% phosphoric acid and acetone 50 parts, was reacted for 24 hours at 40 to 45 ° C, nonvolatile content 67%, epoxy equivalent weight of solids 274 g / e q.
• nopolac type epoxy resin (Epototo YDCN-704, manufactured by Tohto Kasei Co., Ltd.), bisphenol type epoxy resin ( 30 parts of Epicoat 1004) manufactured by Japan Epoxy Resin Co., Ltd. and 100 parts of acetone were added and stirred at 20-25 ° C. to dissolve the epoxy resin in acetone.
• test substrate was produced under the same operation and conditions as in the above Examples:! -7.
• test substrate having the obtained cured film each of PCT resistance, adhesion, solder heat resistance, acid resistance, alkali resistance, non-electrolytic adhesion resistance, and electrical insulation resistance was determined by the test method and evaluation method described later. A test was conducted.
• a glass plate was used in place of the copper through-hole printed wiring board, and processing was performed under the same conditions as described above to determine the water absorption rate.
• Evaluation was performed in the same manner as in the above (8) test method for resistance to electroless gold plating. However, the test was conducted only when the development time was within 180 seconds.
• test substrate was treated with a PCT device (TABAI ESPEC HASTSYSTEM TPC-412MD) under the conditions of 121 ° C and 100% R.H. for 24 hours, and the water absorption rate of the cured film was determined by the following formula.
• PCT device TABAI ESPEC HASTSYSTEM TPC-412MD
• W is the weight of the test board
• W is the weight of the test board after PCT processing
• W is the glass
• ⁇ Water absorption is less than 2%.
• poly-p-hydroxystyrene resin (trade name “Marcalinker 1 ⁇ ”, ⁇ 1 ⁇ equivalent: Maruzen Petrochemical Co., Ltd .: 120) 120 parts, 1.2 parts of potassium hydroxide and 120 parts of toluene were charged, and the system was purged with nitrogen while stirring, and the temperature was raised. Next, 63.8 parts of propylene oxide was gradually added dropwise and reacted at 125 to 132 ° C. and 0 to 4.8 kgZcm 2 for 16 hours.
• reaction solution was cooled to room temperature, and 1.57 parts of 89% phosphoric acid was added to and mixed with the reaction solution to neutralize the hydroxylating power, and the non-volatile content was 62.0% and the hydroxyl equivalent was 182 g / eq.
• a propylene oxide reaction solution of poly_p-hydroxystyrene resin was obtained. This was an average of 1.07 monoleated alkylene oxide per equivalent of phenolic hydroxyl group.
• the resulting poly_p-hydroxystyrene resin alkylene oxide reaction solution (293.0 parts), attalinoleic acid (43.2 parts), methanesulfonic acid (11.53 parts), methylhydroquinone (0.18 parts), and toluene (252.9 parts)
• the mixture was charged into a reactor equipped with a stirrer, a thermometer, and an air blowing tube, and air was blown at a rate of 10 ml / min, and the reaction was carried out at 110 ° C. for 12 hours while stirring.
• the water produced by the reaction was distilled as an azeotrope with toluene, 12.6 parts of water.
• Cresol uni novolak type epoxy resin (Epiclon N-695, Dainippon Ink and Chemicals, Epoxy equivalent 220) 330 parts, gas introduction pipe, stirrer, cooling pipe and thermometer
• 400 parts of canolebitonoreacetate were heated and dissolved by heating to obtain 0.46 parts of quinone of hydride and 1.38 parts of triphenylphosphine.
• the mixture was heated to 95-105 ° C, and 108 parts of acrylic acid was gradually added dropwise to react for 16 hours.
• the reaction product was cooled to 80 to 90 ° C., and 163 parts of tetrahydrophthalic anhydride was added and reacted for 8 hours.
• the thus obtained carboxyleno group-containing photosensitive compound had a non-volatile content of 58% and a solid content acid value of 102 mgK 0 HZg.
• this curable composition is applied onto a support, dried by heating to form a curable composition layer having a thickness of 20 to 30 / im, a cover film is bonded, and the resulting film is stored stably. Sexuality was evaluated.
• test substrate was produced under the same operation and conditions as in the above Examples:! -7.
• test substrate having the obtained cured film each of PCT resistance, adhesion, solder heat resistance, acid resistance, alkali resistance, non-electrolytic adhesion resistance, and electrical insulation resistance was determined by the test method and evaluation method described later. A test was conducted.
• a glass plate was used in place of the copper through-hole printed wiring board, and processing was performed under the same conditions as described above to determine the water absorption rate.
• Evaluation was performed in the same manner as in the above (8) test method for resistance to electroless gold plating. However, the test was conducted only when the development time was within 180 seconds.
• Polyphenol resin manufactured by Japan Epoxy Resin Co., Ltd. which is a condensate of phenols and aromatic aldehydes having a phenolic hydroxyl group, in a photoclave equipped with a thermometer, a nitrogen introduction device / alkylene oxide introduction device and a stirring device.
• Product name “Epicure I Y L6065”, OH fi: 98) 983 ⁇ 4, potassium hydroxide 0 ⁇ 98 parts, and toluene 98 parts were charged, and the system was purged with nitrogen while stirring, and the temperature was raised. Next, 63.8 parts of propylene oxide are gradually added dropwise, 125-: 132. The reaction was carried out at C, 0 to 4.8 kg / cm 2 for 16 hours.
• the reactor was equipped with a thermometer and an air blowing tube, air was blown at a rate of 10 ml / min, and the reaction was carried out at 110 ° C for 12 hours while stirring.
• Water produced by the reaction 9.8 parts of water distilled as an azeotrope with toluene. Thereafter, the mixture was cooled to room temperature, and the resulting reaction solution was neutralized with 29.4 parts of a 15% aqueous sodium hydroxide solution and then washed with water.
• nopolac type epoxy resin (Epototo YDCN-704, manufactured by Tohto Kasei Co., Ltd.), bisphenol type epoxy resin ( 30 parts of Epicoat 1004) manufactured by Japan Epoxy Resin Co., Ltd. and 100 parts of acetone were added and stirred at 20-25 ° C. to dissolve the epoxy resin in acetone.
• this curable composition is applied onto a support, dried by heating to form a curable composition layer having a thickness of 20 to 30 zm, a cover film is bonded, and the resulting film is stored. Stability was evaluated.
• test substrate was produced under the same operation and conditions as in the above Examples:! -7.
• test substrate having the obtained cured film each of PCT resistance, adhesion, solder heat resistance, acid resistance, alkali resistance, non-electrolytic adhesion resistance, and electrical insulation resistance was determined by the test method and evaluation method described later. A test was conducted.
• Evaluation was performed in the same manner as in the above (5) solder heat resistance test method. However, the test was conducted only when the development time was within 180 seconds.
• Evaluation was performed in the same manner as in the above (8) test method for resistance to electroless gold plating. However, the test was conducted only when the development time was within 180 seconds.
• 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 excellent in various properties as described above can be obtained. Not only can it be used advantageously as a resist and its dry film, but also an etching resist, a plating resist, an interlayer insulating layer of a multilayer wiring board, a permanent mask used in the production of tape carrier packages, a resist for a flexible wiring board, a color filter It is also useful for applications such as resist for ink and resist for ink jet.

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