WO2014010204A1 - Résine de type révélateur alcalin, et composition de résine photosensible l'utilisant - Google Patents

Résine de type révélateur alcalin, et composition de résine photosensible l'utilisant Download PDF

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Publication number
WO2014010204A1
WO2014010204A1 PCT/JP2013/004123 JP2013004123W WO2014010204A1 WO 2014010204 A1 WO2014010204 A1 WO 2014010204A1 JP 2013004123 W JP2013004123 W JP 2013004123W WO 2014010204 A1 WO2014010204 A1 WO 2014010204A1
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Prior art keywords
resin
alkali
hydroxyl group
phenol
resin composition
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PCT/JP2013/004123
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English (en)
Japanese (ja)
Inventor
山本　和義
健二 関根
尚文 堀口
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日本化薬株式会社
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Priority to CN201380037427.2A priority Critical patent/CN104470962B/zh
Priority to KR1020157000694A priority patent/KR102031014B1/ko
Priority to JP2014524634A priority patent/JP6111248B2/ja
Publication of WO2014010204A1 publication Critical patent/WO2014010204A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
    • C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
    • C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
    • C08G14/12—Chemically modified polycondensates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
    • C08G8/28—Chemically modified polycondensates
    • C08G8/32—Chemically modified polycondensates by organic acids or derivatives thereof, e.g. fatty oils
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
    • C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
    • C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
    • C08G8/20—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with polyhydric phenols
    • C08G8/22—Resorcinol
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
    • C09D161/34—Condensation polymers of aldehydes or ketones with monomers covered by at least two of the groups C09D161/04, C09D161/18 and C09D161/20
    • 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
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • 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
    • H05K3/0073—Masks not provided for in groups H05K3/02 - H05K3/46, e.g. for photomechanical production of patterned surfaces
    • H05K3/0076—Masks not provided for in groups H05K3/02 - H05K3/46, e.g. for photomechanical production of patterned surfaces characterised by the composition of the mask
    • 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 an alkali developing resin and a photosensitive resin composition containing the same. More specifically, the present invention relates to an alkali developing resin and a photosensitive resin composition used in the field of electronic materials such as a printed wiring board solder resist, a high-density multilayer board interlayer insulating film, and a semiconductor package solder resist.
  • a printed wiring board to which a conventional commercially available alkali development type solder resist is applied is inferior in PCT (Pressure Cooker Test) resistance, which is a long-term reliability test of a package, and the cured product is peeled off.
  • PCT Pressure Cooker Test
  • popcorn phenomenon in which moisture absorbed in the package during the reflow during package mounting due to moisture absorption of the solder resist boils and cracks occur in the solder resist film inside the package and its periphery, is regarded as a problem.
  • Such problems of moisture absorption resistance and long-term reliability are not limited to the above-mentioned mounting technology, but are used for the manufacture of solder resists for general printed wiring boards, flexible printed wiring boards, and tape carrier packages. It is also undesirable in products for other applications such as solder resist and interlayer insulation layers of multilayer wiring boards such as build-up substrates.
  • a photosensitive resin using a novolac type epoxy resin as a starting material has a superior adhesiveness, heat resistance, chemical resistance, electrical insulation, etc. Widely used in many fields.
  • a carboxy group-containing photosensitive resin having excellent heat resistance a resin obtained by reacting a reaction product of a cresol novolac type epoxy resin with an unsaturated group-containing monocarboxylic acid with a polybasic acid anhydride is frequently used. (Patent Document 1).
  • this resin is excellent in heat resistance, there is a problem that cracks due to heat shock are likely to occur because of large shrinkage upon curing, little elongation, and lack of toughness.
  • JP-A-1-54390 Japanese Patent Laid-Open No. 9-54434 Japanese Patent Laid-Open No. 11-288091 Japanese Patent No. 3964326
  • the present invention has been made in view of the above problems, and has a carboxyl group-containing resin from which an ink composition excellent in drying properties can be obtained in addition to various physical properties such as good developability, heat resistance, moisture resistance, and adhesiveness. Is intended to provide. Furthermore, the present invention can form a cured film excellent in various properties required for the following various applications, and can cope with higher density and surface mounting of a printed wiring board, and is developed with a dilute alkaline aqueous solution. An object of the present invention is to provide a liquid curable resin composition having the property of being capable.
  • the phenol resin (a) is represented by the following general formula (1) (In the formula, m1, m2 and m3 are each independently an integer of 1 or 2, and n represents an integer of 0 to 10)
  • the alkali developing resin is 10 to 80% by weight based on the total amount of the composition;
  • the epoxy resin is 1 to 50% by weight based on the total amount of the composition;
  • the photopolymerization initiator is 0.5 to 20% by weight with respect to the total amount of the composition, and
  • the diluent is 10 to 200 parts by weight with respect to 100 parts by weight of the alkali developing resin.
  • the photosensitive resin composition as described in (11) or (12) above, wherein (14) The diluent according to any one of (11) to (13), wherein the polymerizable unsaturated compound is contained as a diluent in an amount of 5 to 200% by weight with respect to 100 parts by weight of the alkali developing resin. Photosensitive resin composition.
  • the photosensitive resin composition according to any one of (11) to (15) above is applied to a printed wiring board to form a coating film, exposed, developed, and then irradiated with ultraviolet rays and / or Alternatively, a method for forming a cured coating film comprising curing by heating.
  • a compound (b) having an alcoholic hydroxyl group and one epoxy group in the molecule is reacted with the hydroxyl group of the phenol resin (a) for producing the alkali developing resin described in (1) above.
  • the photosensitive resin composition of the present invention is excellent in drying property and alkali developability, and the coating film after curing has adhesion, solder heat resistance, electroless gold plating resistance, PCT resistance, flexibility, and thermal shock resistance. Excellent in various characteristics such as HAST characteristics. Since a cured film can be formed at low cost and with high productivity, it can be used for UV-curing printing ink applications that are cured using active energy rays, as well as solder resists, etching resists used in the production of printed wiring boards, Useful for plating resists, interlayer insulating materials, and the like.
  • the phenol resin (a) is used as the skeleton resin.
  • the phenol resin (a) in the present invention means a phenol resin in a broad sense, and means a resin having at least two phenolic hydroxyl groups in one molecule. Therefore, as the phenol resin (a), a phenol resin having at least two phenolic hydroxyl groups in one molecule is used. As this phenol resin (a), all phenol resins such as resol type, novolak type and cresol type can be used.
  • an epoxy-modified type obtained by modifying a polyfunctional phenol compound with an epoxy compound, a phenol-added butadiene (co) polymer obtained by adding a phenol to a butadiene (co) polymer, a polymer resin of phenols and dicyclopentadiene, Polymerized resins of phenols and biphenyl can also be used.
  • modified novolak type phenol resins such as novolak type phenol resins such as phenol novolak resin, cresol novolak resin, biphenyl novolak type resorcin resin, paraxylylene modified novolak resin, metaxylylene modified novolak resin, orthoxylylene modified novolak resin, etc.
  • Bisphenol compounds such as bisphenol A and bisphenol F; biphenyl type phenol resins; resol type phenol resins; aralkyl type phenol resins such as phenol aralkyl resins and biphenyl aralkyl type phenol resins; alkane types such as triphenol alkane type resins and polymers thereof; Phenolic resin; naphthalene ring-containing phenolic resin, dicyclopentadiene modified phenolic resin, alicyclic phenolic resin, heterocyclic pheno Resins. These phenol resins may be used alone or in combination of two or more.
  • the phenol resin (a) has a molecular weight of about 300 to 30,000, preferably about 400 to 15,000. As the molecular weight of the resin, a number average molecular weight or a weight average molecular weight is used.
  • a novolak type phenol resin can be exemplified, more preferably, a phenol resin having a cresol skeleton or a biphenyl skeleton in the structure thereof can be exemplified, and more preferably biphenyl.
  • a phenol resin having a skeleton can be given.
  • examples of the novolak type phenol resin having a cresol skeleton include a cresol type novolak resin
  • examples of the phenol resin having a biphenyl skeleton include a biphenyl aralkyl type phenol resin and a biphenyl novolac type phenol resin.
  • a novolak type phenolic resin containing a biphenyl skeleton More preferred is a novolak type phenolic resin containing a biphenyl skeleton, and more preferred is the following general formula (1) (In the formula, m1, m2 and m3 are each independently an integer of 1 or 2, and n represents an integer of 0 to 10) It is a phenol resin (a1) represented by these.
  • phenol resin (a1) of the general formula (1) (hereinafter also simply referred to as phenol resin (a1))
  • a phenol resin having a ring (preferably resorcin structure) is more preferable.
  • the ratio of the number of hydroxyl groups in the benzene ring having two hydroxyl groups (preferably resorcin structure) to the total number of phenolic hydroxyl groups in the phenol resin (a1) is preferably 5 to 100%. This ratio is a ratio calculated from the molar ratio of phenol and dihydroxybenzene (preferably resorcin) used in the synthesis of the phenol resin (a1).
  • the hydroxyl equivalent of the phenol resin (a1) is about 70 to 170 g / eq, and in some cases about 102 to 140 g / eq.
  • the hydroxyl equivalent of the phenol resin can be measured by a conventional method.
  • the compound (b) having an alcoholic hydroxyl group and one epoxy group in the molecule to be reacted with the phenol resin (a) is known as long as it is a compound having an alcoholic hydroxyl group and one epoxy group in the molecule.
  • These include glycidol or monoglycidyl ether of glycol having 2 to 4 carbon atoms such as ethylene glycol monoglycidyl ether. In the present invention, glycidol is particularly preferable.
  • the compound (b) is preferably used in an amount of 0.1 to 0.9 mol, more preferably 1 equivalent to 1 equivalent of the phenolic hydroxyl group of the phenol resin (a).
  • the compound (b) is added in a proportion of 0.1 to 0.7 mol, or a proportion of 0.1 to 0.6 mol, relative to 1 equivalent of the phenolic hydroxyl group of the phenol resin (a). Furthermore, it is very preferable to carry out the reaction at a ratio of 0.2 to 0.6 mol. If the amount of the compound (b) is too large, the water solubility of the resin X of the present invention obtained by reacting the following polybasic acid anhydride (c) becomes too high, and the resin composition containing the resin X The water resistance of the cured product may be lowered. In this reaction, the epoxy group of the compound (b) undergoes ring-opening addition to the phenolic hydroxyl group of the phenol resin (a) to form an ether bond, and a secondary alcoholic hydroxyl group is formed.
  • the polybasic acid anhydride (c) reacts with the alcoholic hydroxyl group in the intermediate X to form a phenolic compound. This is because it does not react with a hydroxyl group.
  • a solvent can be used for the reaction of the phenol resin (a) and the compound (b).
  • solvents can be used such as ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; dipropylene glycol dimethyl ether, dipropylene glycol dimethyl ether and dipropylene glycol.
  • Glycol ethers such as dimethyl ether and dipropylene glycol diethyl ether; ethyl acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl Ether acetate, butyl acetate
  • Organic solvents such as esters such as sorb acetate and carbitol acetate; aliphatic hydrocarbons such as octane and decane; petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha; .
  • reactivity such as carbitol (meth) acrylate, pentaerythritol tetra (meth) acrylate, trimethylolpropane (meth) acrylate, tris (hydroxyethyl) isocyanurate tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc.
  • Monomers can also be used.
  • a catalyst in order to promote the reaction between the phenol resin (a) and the compound (b).
  • a known catalyst can be used as a reaction catalyst between an epoxy group and a phenolic hydroxyl group.
  • catalysts include triethylamine, benzyldimethylamine, methyltriethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstibine, chromium octoate, zirconium octoate and the like. Can do.
  • the amount of such a catalyst used is preferably 0.01 to 1% by weight based on the reaction raw material mixture.
  • the reaction temperature is preferably 60 to 150 ° C.
  • the reaction time is preferably 5 to 24 hours. In this way, intermediate X can be obtained.
  • Resin Y is obtained by further reacting the polybasic acid anhydride (c) with the hydroxyl group (alcoholic hydroxyl group) of intermediate X obtained as described above.
  • the polybasic acid anhydride (c) include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methyltetra
  • dibasic acid anhydrides such as hydrophthalic anhydride and chlorendic anhydride
  • polybasic acid anhydrides such as trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, and biphenyltetracarboxylic anhydride.
  • monoanhydrides are preferred, and in particular, polybasic acid anhydrides having 2 or 3 carboxy groups such as trimellitic anhydride, tetrahydrophthalic anhydride, succinic anhydride, hexahydrophthalic anhydride, and the like are more preferred.
  • it is a polybasic acid monoanhydride having 2 or 3 carboxy groups on a hydrocarbon having 2 to 6 carbon atoms, more preferably 2 or 3 carboxy groups on a carbon 6-membered ring.
  • It is a monobasic acid polyanhydride.
  • the carbon 6-membered ring may be an aromatic ring or an aliphatic ring.
  • trimellitic anhydride or tetrahydrophthalic anhydride is preferred.
  • the resin Y For the production of the resin Y, usually 0.05 to 0.9 mol of saturated or unsaturated polybasic acid anhydride (c) is used per 1 equivalent of the hydroxyl group (alcoholic hydroxyl group) in the intermediate X.
  • the reaction is performed at a rate of Preferably, the saturated or unsaturated polybasic acid anhydride (c) is used in an amount of 0.1 to 0.8 mol, more preferably 0.8, per 1 equivalent of the hydroxyl group (alcoholic hydroxyl group) in the intermediate X.
  • the reaction is carried out at a ratio of 1 to 0.7 mol.
  • the ratio of the number of phenolic hydroxyl groups remaining in the resin Y to the number of phenolic hydroxyl groups of the raw material phenol resin (a) (total number of phenolic hydroxyl groups) is that the reaction proceeds substantially quantitatively. It can be calculated from the amount of raw material charged.
  • Resin Y was used for the photosensitive resin composition, Resin Y with a large amount of residual phenolic hydroxyl group was judged to be advantageous for improving the heat resistance of the cured product.
  • the resin Y has a carboxy group introduced by the reaction with the polybasic acid anhydride (c).
  • the preferred resin Y of the present invention is a resin containing the remaining phenolic hydroxyl group, carboxy group, and alcoholic hydroxyl group remaining without reacting with the polybasic acid anhydride (c).
  • Examples of the preferred resin Y of the present invention are as follows. I. Reaction obtained by reacting a compound (b) having an alcoholic hydroxyl group and one epoxy group in the molecule at a ratio of 0.1 to 0.9 mol with respect to 1 equivalent of the hydroxyl group of the phenol resin (a). The hydroxyl group (alcoholic hydroxyl group) in the product X is further filled with 0% of saturated and / or unsaturated polybasic acid anhydride (c) with respect to 1 equivalent of the hydroxyl group (alcoholic hydroxyl group) in the reaction product X. Alkali-developable resin obtained by reacting at a ratio of 0.05 to 0.9 mol. II.
  • the present invention further includes a photosensitive resin composition
  • a photosensitive resin composition comprising (A) the resin Y of the present invention, (B) an epoxy resin, (C) a photopolymerization initiator, and (D) a diluent. It is related.
  • An embodiment containing a polymerizable unsaturated compound such as a (meth) acrylate compound as the diluent is particularly preferred.
  • the amount of the resin Y contained in the photosensitive resin composition of the present invention is preferably about 10 to 80% by weight, more preferably about 15 to 60% by weight, based on the total amount of the photosensitive resin composition. It is preferably 30 to 60% by weight.
  • epoxy resin (B) used in the photosensitive resin composition of the present invention those having two or more epoxy groups in one molecule are usually used.
  • Epoxy resin obtained epoxy resin obtained by reacting polyfunctional hydroxynaphthalene with epichlorohydrin, silicone modified epoxy resin, ⁇ -caprolactone modified epoxy resin, glycidylamine type epoxy obtained by reaction of epichlorohydrin with primary or secondary amine
  • examples thereof include resins and heterocyclic epoxy resins such as triglycidyl isocyanate.
  • One or more of these epoxy resins may be used in combination. It is also effective to use an isocyanate-modified epoxy resin for the purpose of improving toughness after securing the glass transition point Tg, or to use a phosphorus-containing epoxy resin from the viewpoint of imparting flame retardancy.
  • the epoxy resin (B) is blended in the composition as a thermosetting component in order to improve various properties as a solder resist such as adhesion, heat resistance, and plating resistance, and is rarely used in the production of printed wiring boards and the like. After developing with an alkaline aqueous solution, the resin is cured by heating to give better adhesion to a wiring board, heat resistance, plating resistance, and the like.
  • the photopolymerization initiator (C) may be used in combination with a known photosensitizer such as a tertiary amine.
  • a known photosensitizer such as a tertiary amine.
  • Specific examples include triethanolamine, tripropanolamine, triethylamine, N, N-dimethylamino acid benzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, pentyl-4-dimethylaminobenzoate, and the like.
  • a polymerizable unsaturated compound and / or a solvent is used as a diluent (D).
  • the polymerizable unsaturated compound and / or solvent used as the diluent (D) is for the purpose of improving curability to active energy rays and / or coating properties when a photosensitive resin composition is used as a resist ink. It is what you use.
  • ⁇ Adhesion> According to the test method of JIS D 0202, a cross cut was put in a grid pattern on the cured film of each test piece, and then a peeling test with a cellophane tape was performed to visually determine the state of peeling after the test. Evaluation was performed according to the following criteria. ⁇ : No peeling at all. ⁇ : The cross-cut portion is slightly peeled off. X: The coating film has peeling.
  • Example 1 Example 2
  • Example 3 Comparative Example 1 20 ⁇ ⁇ ⁇ ⁇ 40 ⁇ ⁇ ⁇ ⁇ 60 ⁇ ⁇ ⁇ ⁇ 80 ⁇ ⁇ ⁇ ⁇ 100 ⁇ ⁇ ⁇ ⁇ 120 ⁇ ⁇ ⁇ ⁇
  • Synthesis Example 4 (Synthesis Example of Resin Y-4): A biphenyl novolac-type resorcin resin (hydroxyl equivalent 102, softening point 85.2 ° C.) 102 parts (1.0 equivalent) synthesized according to Example 1 of JP-A-7-292066 and propylene glycol monomethyl ether acetate 192.09 parts were charged. The mixture was uniformly dissolved by heating to 80 ° C. After confirming dissolution, 37.04 parts (0.5 mol) of glycidol and 0.42 parts of triphenylphosphine were added thereto, and the mixture was heated to 120 ° C.
  • Examples 4-7 and Comparative Example 2 Using each of the resins Y-2, Y-3, Y-4 and the curable resin Z obtained from the synthesis examples 2, 3, 4 and the comparative synthesis example 1, according to the blending ratio shown in Table 4. It knead
  • the compositions of Examples 4 to 7 and Comparative Example 2 prepared at the blending ratios shown in Table 4 were diluted with methyl ethyl ketone, applied onto a PET film, dried at 80 ° C. for 30 minutes, and a dry film having a thickness of 20 ⁇ m. A photosensitive resin composition layer was prepared. Furthermore, after preliminary drying at 80 ° C.
  • the alkali-developable resin of the present invention is superior to conventionally known epoxy-based photosensitive resins in terms of drying and alkali developability, and the cured product is in close contact. Excellent in heat resistance, solder heat resistance, electroless gold plating resistance, PCT resistance, flexibility, thermal shock resistance, HAST characteristics, and the like.
  • the alkali-developable resin of the present invention containing a biphenyl novolac-type resorcin-containing phenolic resin is superior to others in dryness and alkali-developability among the alkali-developable resins of the present invention.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Organic Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
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  • Oil, Petroleum & Natural Gas (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
  • Materials For Photolithography (AREA)
  • Phenolic Resins Or Amino Resins (AREA)
  • Non-Metallic Protective Coatings For Printed Circuits (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Epoxy Resins (AREA)

Abstract

Cette invention concerne une résine de type révélateur alcalin qui est obtenue par réaction d'un composé (b) ayant un groupe hydroxyle de type alcool et un groupe époxy dans la molécule avec les groupes hydroxyle d'une résine phénolique (a), puis réaction des groupes hydroxyle dans le produit réactionnel X obtenu avec un anhydride d'acide polybasique (c) saturé et/ou insaturé ; et concerne une composition de résine photosensible contenant (A) ladite résine de type révélateur alcalin, (B) une résine époxy; (C) un amorceur de photopolymérisation, et (D) un diluant. Ladite composition de résine possède d'excellentes propriétés de séchage et aptitude à la révélation alcaline, et le film de revêtement obtenu après durcissement est remarquable du point de vue de diverses caractéristiques telles que l'adhérence, la résistance à la chaleur de soudage, la résistance au dépôt d'or autocatalytique, la résistance PCT, le flexibilité, la résistance au choc thermique, et les caractéristiques HAST, et est utile à titre de réserve pour soudage, réserve pour gravure, réserve pour placage, ou à titre de matériau isolant intercouche utilisé lors de la fabrication de cartes de câblage imprimées.
PCT/JP2013/004123 2012-07-13 2013-07-03 Résine de type révélateur alcalin, et composition de résine photosensible l'utilisant WO2014010204A1 (fr)

Priority Applications (3)

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CN201380037427.2A CN104470962B (zh) 2012-07-13 2013-07-03 碱显影型树脂、使用该树脂的感光性树脂组合物
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2016006264A1 (ja) * 2014-07-10 2017-04-27 太陽インキ製造株式会社 樹脂絶縁層の形成方法、樹脂絶縁層およびプリント配線板
JP2018035332A (ja) * 2015-12-28 2018-03-08 荒川化学工業株式会社 変性フェノール樹脂、活性エネルギー線硬化型樹脂組成物、ゲルワニス、硬化物、活性エネルギー線硬化型印刷インキ及び印刷物
TWI708528B (zh) * 2014-02-19 2020-10-21 日商味之素股份有限公司 樹脂薄片
KR20210049870A (ko) 2018-08-28 2021-05-06 스미또모 베이크라이트 가부시키가이샤 네거티브형 감광성 수지 조성물, 및 그것을 이용한 반도체 장치

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI687769B (zh) * 2015-05-12 2020-03-11 日商三菱製紙股份有限公司 噴砂用感光性樹脂組成物及噴砂處理方法
TWI609382B (zh) * 2016-07-26 2017-12-21 台灣太陽油墨股份有限公司 介電材料組成物及含其之絕緣膜及電路板
CN110753455A (zh) * 2019-10-23 2020-02-04 深南电路股份有限公司 一种抗镀干膜加工方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002024774A1 (fr) * 2000-09-20 2002-03-28 Taiyo Ink Manufacturing Co., Ltd. Resine photosensible carboxylee, composition photodurcissable/thermodurcissable pouvant etre developpee par une solution alcaline et contenant cette resine, et article durci produit a partir de ces elements
JP2002128865A (ja) * 2000-10-31 2002-05-09 Showa Highpolymer Co Ltd 感光性樹脂組成物
JP2002138125A (ja) * 2000-10-31 2002-05-14 Showa Highpolymer Co Ltd 硬化性樹脂及び感光性樹脂組成物
WO2003070800A1 (fr) * 2002-02-19 2003-08-28 Taiyo Ink Manufacturing Co., Ltd. Resine durcissable et composition contenant la resine durcissable

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6454390A (en) 1987-08-26 1989-03-01 Matsushita Electric Ind Co Ltd Driver using shape memory alloy
JP3190251B2 (ja) 1995-06-06 2001-07-23 太陽インキ製造株式会社 アルカリ現像型のフレキシブルプリント配線板用光硬化性・熱硬化性樹脂組成物
JP3659825B2 (ja) 1997-12-19 2005-06-15 太陽インキ製造株式会社 アルカリ現像可能な光硬化性・熱硬化性組成物及びそれから得られる硬化皮膜
JP3468291B2 (ja) * 2000-04-10 2003-11-17 荒川化学工業株式会社 アルコキシ基含有シラン変性フェノール樹脂、樹脂組成物、エポキシ樹脂硬化剤及び有機・無機ハイブリッド体。
JP2002128866A (ja) * 2000-10-20 2002-05-09 Toshiba Chem Corp 導電性ペースト
JP2002138126A (ja) * 2000-10-31 2002-05-14 Inoac Corp 弾性部材
WO2011122027A1 (fr) * 2010-03-31 2011-10-06 太陽ホールディングス株式会社 Composition de résine thermodurcissable photodurcissable

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002024774A1 (fr) * 2000-09-20 2002-03-28 Taiyo Ink Manufacturing Co., Ltd. Resine photosensible carboxylee, composition photodurcissable/thermodurcissable pouvant etre developpee par une solution alcaline et contenant cette resine, et article durci produit a partir de ces elements
JP2002128865A (ja) * 2000-10-31 2002-05-09 Showa Highpolymer Co Ltd 感光性樹脂組成物
JP2002138125A (ja) * 2000-10-31 2002-05-14 Showa Highpolymer Co Ltd 硬化性樹脂及び感光性樹脂組成物
WO2003070800A1 (fr) * 2002-02-19 2003-08-28 Taiyo Ink Manufacturing Co., Ltd. Resine durcissable et composition contenant la resine durcissable

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI708528B (zh) * 2014-02-19 2020-10-21 日商味之素股份有限公司 樹脂薄片
JPWO2016006264A1 (ja) * 2014-07-10 2017-04-27 太陽インキ製造株式会社 樹脂絶縁層の形成方法、樹脂絶縁層およびプリント配線板
JP2018035332A (ja) * 2015-12-28 2018-03-08 荒川化学工業株式会社 変性フェノール樹脂、活性エネルギー線硬化型樹脂組成物、ゲルワニス、硬化物、活性エネルギー線硬化型印刷インキ及び印刷物
KR20210049870A (ko) 2018-08-28 2021-05-06 스미또모 베이크라이트 가부시키가이샤 네거티브형 감광성 수지 조성물, 및 그것을 이용한 반도체 장치

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JPWO2014010204A1 (ja) 2016-06-20
TW201420668A (zh) 2014-06-01
KR102031014B1 (ko) 2019-10-11
JP6111248B2 (ja) 2017-04-05
CN104470962A (zh) 2015-03-25

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