WO2012029806A1 - Method for producing photosensitive resin and photosensitive resin composition - Google Patents

Method for producing photosensitive resin and photosensitive resin composition Download PDF

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Publication number
WO2012029806A1
WO2012029806A1 PCT/JP2011/069647 JP2011069647W WO2012029806A1 WO 2012029806 A1 WO2012029806 A1 WO 2012029806A1 JP 2011069647 W JP2011069647 W JP 2011069647W WO 2012029806 A1 WO2012029806 A1 WO 2012029806A1
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Prior art keywords
resin
group
hydroxyl group
photosensitive resin
polymerizable unsaturated
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PCT/JP2011/069647
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French (fr)
Japanese (ja)
Inventor
坂本　淳
浩志 上井
幸志 小川
将行 小林
将司 西口
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昭和電工株式会社
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Application filed by 昭和電工株式会社 filed Critical 昭和電工株式会社
Priority to KR1020137004223A priority Critical patent/KR101468341B1/en
Priority to CN201180042400.3A priority patent/CN103080168B/en
Priority to JP2012531902A priority patent/JP5875519B2/en
Publication of WO2012029806A1 publication Critical patent/WO2012029806A1/en

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Classifications

    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • 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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable

Definitions

  • a polymerizable unsaturated group is converted into zinc or zinc by a transesterification reaction between a resin in which a phenolic hydroxyl group of a resin having a phenolic hydroxyl group is chain-extended with a (poly) oxyalkylene group and a polymerizable unsaturated group-containing carboxylic acid ester.
  • the present invention relates to a method for producing a photosensitive resin that is introduced in the presence of an acetylacetone complex of zirconium and reacts the resulting reaction product with a polybasic acid anhydride, and a photosensitive resin composition containing the resin.
  • Patent Document 1 describes a carboxyl group-containing photosensitive resin composition using a phenol resin and alkylene oxides having improved toughness and heat resistance.
  • the photosensitive resin made from epoxy resin contains a lot of chlorine derived from the manufacturing method of epoxy resin, but the photosensitive resin using phenol resin and alkylene oxides mentioned above uses chlorine in the manufacturing process. Therefore, the chlorine content is extremely low.
  • these use catalysts such as strong acids when introducing unsaturated monocarboxylic acids, so they are highly corrosive to metals such as stainless steel, narrowing the range of materials that can be used in production equipment, and increasing equipment costs. Was invited.
  • metal components generated by corrosion are mixed in the resin, the reliability as a solder resist such as electrical insulation is greatly adversely affected.
  • Patent Document 2 describes the introduction of a polymerizable unsaturated group using an unsaturated group-containing carboxylic acid ester, but its esterification catalyst is also a strongly acidic compound and does not solve the above-described problems.
  • Patent Document 3 discloses a method for producing an acrylic monomer represented by a specific formula by reacting a lower alkyl ester of (meth) acrylic acid with a dialkylamino alcohol in the presence of a metal acetylacetone complex, It is disclosed that this acrylic monomer is useful as a material such as a polymer flocculant and a conductive processing agent.
  • Patent No. 3964326 Japanese Patent No. 3974875 Japanese Patent Laid-Open No. 01-180861
  • the object of the present invention is to reduce the content of chlorine and metal corrosive components in order to achieve high reliability of the printed wiring board, and to adhere the cured film, It is to provide a method for producing a photosensitive resin excellent in other required characteristics such as solder heat resistance, moisture absorption resistance, PCT resistance, electrical insulation, etc., and a photosensitive resin containing a photosensitive resin by this production method. It is providing a functional resin composition.
  • the present invention (1) Resin having a chain extended with a (poly) oxyalkylene group having an alcoholic hydroxyl group at a part or all of the phenolic hydroxyl group of a resin (a) having two or more phenolic hydroxyl groups in one molecule (b)
  • the polymerizable unsaturated group-containing carboxylic acid ester (c) is added to 1 equivalent of the alcoholic hydroxyl group of the resin (b) in the presence of the acetylacetone complex (d) of zinc or zirconium.
  • the amount of the phenolic hydroxyl group remaining in the resin (b) is 0.2 equivalent or less with respect to 1 equivalent of the phenolic hydroxyl group of the resin (a), (1) or (2) Manufacturing method of photosensitive resin, (4)
  • a photosensitive resin comprising a photosensitive resin, an epoxy resin, a photopolymerization initiator, and a polymerizable unsaturated compound and / or solvent obtained by the production method according to any one of (1) to (3) A composition is provided.
  • the photosensitive resin obtained by the production method of the present invention is not only excellent in adhesion, solder heat resistance and PCT resistance, but also has stable electrical characteristics at high temperature and high humidity.
  • this manufacturing method is not limited to the material of the reaction apparatus used, and it is not necessary to perform catalyst cleaning such as complicated water washing, so that the manufacturing process can be simplified and the desired photosensitive resin can be obtained efficiently. This is very advantageous industrially.
  • the resin (b) in the present invention is generally a method in which an alkylene oxide or the like is reacted with a resin (a) having two or more phenolic hydroxyl groups in one molecule under a catalyst, and has an alcoholic hydroxyl group at the terminal. It can be obtained by introducing a (poly) oxyalkylene group. Moreover, although it can manufacture also with a cyclic carbonate etc. instead of an alkylene oxide, it is not limited to these.
  • the resin (a) having two or more phenolic hydroxyl groups in one molecule includes a condensate of phenols and ketones, a condensate of phenols and aldehydes, and an aromatic having phenols and phenolic hydroxyl groups.
  • examples include, but are not limited to, condensates with aldehydes, poly-p-hydroxystyrene, naphthol type novolac resins, trisphenol methane type resins, and the like.
  • the substitution position of each substituent in the compound is not particularly limited, and all substitutable isomers that can be substituted can be used in the present invention. These may be used alone or in combination of two or more.
  • the (poly) oxyalkylene group having an alcoholic hydroxyl group at the terminal preferably has 2 to 6 carbon atoms in the oxyalkylene unit.
  • the hydrocarbon group include ethylene, propylene, butylene, pentylene, Examples include, but are not limited to, linear or branched alkylene groups such as hexylene, methylpropylene, and propylethylene.
  • the (poly) oxyalkylene group is chain-extended from part or all of the phenolic hydroxyl group of the resin (a), and the residual phenolic group to which no (poly) oxyalkylene group is added in the resin (b) It is preferable that a hydroxyl group is 0.2 equivalent or less with respect to the phenolic hydroxyl group of the said resin (a).
  • the residual phenolic hydroxyl group is more than 0.2 equivalents relative to the resin (a)
  • the reactivity with the polymerizable unsaturated group-containing carboxylic acid ester (c) is deteriorated, and the amount of polymerizable unsaturated groups introduced is reduced. May be low.
  • the number of repeating oxyalkylene units is preferably 1-10. When the number of repeating oxyalkylene units is less than 1, the photocurability of the photosensitive resin of the present invention may be poor. Further, when the number of repeating oxyalkylene units is more than 10, there is a fear that the heat resistance is lowered and the photocurability and the thermosetting property are poor.
  • a polymerizable unsaturated group can be introduced into the resin (b) by reacting the polymerizable unsaturated group-containing carboxylic acid ester (c) with the resin (b) in the presence of the catalyst (d) by a transesterification reaction. it can.
  • the polymerizable unsaturated group-containing carboxylic acid ester (c) in the present invention is preferably a (meth) acrylic acid ester, specifically, methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, acrylic acid.
  • the amount of the polymerizable unsaturated group introduced is 0.2 to 0.8 equivalents relative to 1 equivalent of the alcoholic hydroxyl group of the resin (b) (for example, in the case of (meth) acrylic acid ester, the resin (b) 0.2 to 0.8 mol) is preferable with respect to 1 mol of alcoholic hydroxyl group, and more preferably 0.4 to 0.6 equivalent.
  • the introduction amount of the polymerizable unsaturated group is less than 0.2 equivalent, the curability is insufficient, the fine pattern cannot be obtained, the flexibility of the cured coating film is difficult to obtain, and the curing time is preferably increased. Absent.
  • the introduction amount of the polymerizable unsaturated group is larger than 0.8 equivalent, since the alcoholic hydroxyl group that reacts with the polybasic acid anhydride decreases, the alkali developability deteriorates.
  • transesterification catalyst (d) used in the present invention an acetylacetone complex of zinc and zirconium is used. Specific examples thereof include bispentadionato zinc (Zn (acac) 2 ) and tetrakispentadionato zirconium (Zr (acac) 4 )). These catalysts may be anhydrous or hydrated, and commercially available ones can be used as they are.
  • the amount used is preferably 0.1 to 10 parts by mass per 100 parts by mass of (b).
  • the catalyst may be charged all at once, but may be added in several batches. When the amount of catalyst is less than 0.1 parts by mass, the reaction does not proceed easily, and there is no particular advantage even if the amount exceeds 10 parts by mass.
  • the reaction temperature is 50 to 150 ° C., preferably 80 to 130 ° C., and the reaction time is usually 1 to 10 hours, although it varies depending on the type and amount of raw materials used, pressure, temperature, catalyst amount and the like.
  • the reaction can be performed without solvent or in the presence of a solvent.
  • the type of solvent that can be used is not particularly limited as long as it is inert to the unsaturated group-containing carboxylic acid ester, catalyst, and reaction product of the raw material.
  • Aromatic hydrocarbons such as benzene, toluene and xylene, aliphatic and alicyclic hydrocarbons such as n-hexane, n-heptane and cyclohexane, ethers such as dioxane, diisopropyl ether and tetrahydrofuran, Examples thereof include nitriles such as acetonitrile and propionitrile.
  • the polymerizable unsaturated group-containing carboxylic acid ester is used as an azeotropic agent with the alcohol as a by-product to further distill off the alcohol. It can also be done quickly.
  • the raw material polymerizable unsaturated group-containing carboxylic acid ester has polymerizability
  • a known polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, phenothiazine or the like can be used. It is also effective to use oxygen molecules as a polymerization inhibitor. In this case, a method in which air is sent into the reaction solution and accompanied by by-produced alcohol is preferable.
  • the esterification rate can be controlled by measuring the esterification rate during the reaction and stopping the reaction at an arbitrary esterification rate.
  • the resin is sampled during the reaction, the amount of ester groups and hydroxyl groups is measured by NMR or IR, and the activity of the catalyst is increased by adding carboxylic acids such as acetic acid and acrylic acid when the desired esterification rate is reached.
  • the amount of the polymerizable unsaturated group introduced can be controlled by stopping the esterification exchange reaction.
  • washing with water or the like may be performed as necessary to remove the catalyst.
  • an additive such as acetic acid, acrylic acid, or MeOH may be added to such an extent that the catalyst is easily dissolved in the washing water without causing an influence such as corrosion of the production apparatus.
  • the curable resin which is a reaction product of the resin (b) and the polymerizable unsaturated group-containing carboxylic acid ester (c), is reacted with the polybasic acid anhydride (e) to improve the developability in an aqueous alkali solution.
  • the carboxyl group-containing curable resin shown can be obtained.
  • Usable polybasic acid anhydrides include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methyl
  • Examples include dibasic acid anhydrides such as tetrahydrophthalic anhydride and chlorendic anhydride, polybasic acid anhydrides such as trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, and biphenyltetracarboxylic anhydride.
  • tetrahydrophthalic anhydride, succinic anhydride, and hexahydrophthalic anhydride are preferably used.
  • the reaction amount of the polybasic acid anhydride (e) is 0.1 to 1.0 equivalent of polybasic acid anhydride (for example, tetrahydrophthalic anhydride, succinic anhydride) with respect to 1 equivalent of residual alcoholic hydroxyl group in the resin.
  • a dibasic acid anhydride such as acid or hexahydrophthalic anhydride
  • Equivalent amounts should be used. If the addition amount of the polybasic acid anhydride is less than 0.1 equivalent, sufficient alkali developability cannot be obtained, and if it exceeds 1.0 equivalent, the electric properties of the cured coating film may be deteriorated.
  • the photosensitive resin obtained by the production method of the present invention provides a photosensitive resin composition containing an epoxy resin, a photopolymerization initiator, and a polymerizable unsaturated compound and / or a solvent, and is used for applications such as resist inks. Can do.
  • Examples of the epoxy resin include those having two or more epoxy groups in one molecule, and are bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, phenol novolac type epoxy resin, cresol novolak.
  • Type epoxy resin dicyclopentadiene-phenol novolac type epoxy resin, phenol-cresol novolac co-condensation type epoxy resin, bisphenol A novolac type epoxy resin, bisphenol F novolac type epoxy resin or their halogenated epoxy compounds, triphenylol methane type Epichlorohydrin is reacted with polyfunctional phenol such as epoxy resin, alkyl-substituted triphenylol methane type epoxy resin, tetraphenylol ethane type epoxy resin, etc.
  • An epoxy resin obtained by reacting a polyfunctional hydroxynaphthalene epichlorohydrin, a silicone-modified epoxy resin, an ⁇ -caprolactone-modified epoxy resin, a glycidylamine-type epoxy resin obtained by reaction of epichlorohydrin with a primary or secondary amine examples include heterocyclic epoxy resins such as triglycidyl isocyanate. One or two or more of these epoxy resins may be used in combination.
  • epoxy resins are used in an amount of 3 to 100 parts by weight, preferably 6 to 75 parts by weight, based on 100 parts by weight of the photosensitive resin obtained by the production method of the present invention.
  • the epoxy resin is less than 3 parts by mass, the carboxyl group in the photosensitive resin obtained by the production method of the present invention is not satisfied with the amount that substantially reacts, so that the water resistance, alkali resistance, and electrical characteristics are deteriorated. Absent.
  • the amount exceeds 100 parts by mass, a linear polymer having an unreacted epoxy group is generated, so that the heat resistance and the solvent resistance become insufficient.
  • benzoin and its derivatives such as benzoin, benzoin methyl ether, benzoin isopropyl ether and benzoin isobutyl ether, benzyl ketal and its derivatives such as benzyldimethyl ketal, acetophenone, 2,2-dimethoxy-2 -Phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4-methylthiophyl) -2-morpholinopropane-1 Acetophenone and its derivatives such as -one, anthraquinone and its derivatives such as 2-methylanthraquinone, 2-chloroanthraquinone, 2-ethylanthraquinone and 2-t-butylanthraquinone, thio Examples thereof include thioxanthone such as benzoin, benzoin methyl ether
  • the photopolymerization initiating effect is promoted by using various amine compounds in combination with these photopolymerization initiators as required, and they can be used in combination in the present invention.
  • the amount of the photopolymerization initiator used is 0.1 to 20 parts by mass, preferably 1 to 10 parts by mass, with respect to 100 parts by mass of the photosensitive resin obtained by the production method of the present invention.
  • the polymerizable unsaturated compound and / or the solvent is used for the purpose of improving the curability to active energy rays and / or the coating property when the photosensitive resin composition is used as a resist ink.
  • the polymerizable unsaturated compound is preferably an active energy light curable monomer, such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, N-pyrrolidone, N-acryloylmorpholine, N, N-dimethylacrylamide, N , N-diethylacrylamide, N, N-dimethylaminoethyl acrylate, N, N-dimethylaminopropyl acrylate, methoxypolyethylene glycol acrylate, ethoxypolyethylene glycol acrylate, melamine acrylate, phenoxyethyl acrylate, phenoxypropyl acrylate, ethylene glycol diacrylate, Dipropylene glycol diacrylate, polydipropylene glycol diacrylate, trimethylolpropane triacrylate DOO, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hex
  • ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone
  • aromatic hydrocarbons such as toluene and xylene
  • carbitols such as ethyl cellosolve, butyl cellosolve, carbitol and butyl carbitol, ethyl acetate and butyl acetate
  • Cellosolve acetate, butyl cellosolve acetate, carbitol acetate and the like may be used alone or in combination of two or more.
  • the polymerizable unsaturated compound or solvent is used alone or as a mixture of two or more.
  • the amount of the polymerizable unsaturated compound and / or solvent used is 10 to 200 parts by weight, preferably 20 to 150 parts by weight, based on 100 parts by weight of the photosensitive resin obtained by the production method of the present invention.
  • the amount of the polymerizable unsaturated compound used is less than 10 parts by mass, the photosensitivity is too low.
  • the viscosity becomes too low when the photosensitive resin composition is used as a resist ink. Resistance as a coating film becomes insufficient.
  • inorganic fillers such as silica, calcium carbonate, barium sulfate, clay, talc, phthalocyanine green, phthalocyanine blue
  • various additives such as antifoaming agents and leveling agents, polymerization inhibitors such as hydroquinone, resorcinol, catechol, pyroganol, hydroquinone monomethyl ether, t-butylcatechol, and phenothiazine are used. May be.
  • a low-pressure mercury lamp As the irradiation light source for curing the photosensitive resin composition of the present invention, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, a xenon lamp, a metal halide lamp and the like are suitable.
  • a laser beam can also be used.
  • Example 1 A reaction vessel made of SUS (stainless steel) equipped with a stirrer, cooling tube, thermometer, and air introduction tube reacts with Novolac-type cresol resin (trade name “Shornol BRG-556”) manufactured by Showa Polymer Co., Ltd.
  • SUS stainless steel
  • thermometer thermometer
  • air introduction tube reacts with Novolac-type cresol resin (trade name “Shornol BRG-556”) manufactured by Showa Polymer Co., Ltd.
  • the ratio of the value was set to 100%, and the ratio of the integrated value of the peak of the aromatic ring of the resin during the reaction or after completion of the reaction and the peak of the introduced polymerizable unsaturated group was measured to determine the ratio of the polymerizable unsaturated group.
  • the amount introduced was calculated.
  • the obtained resin solution is combusted by an automatic sample combustion apparatus AQF-100 (manufactured by Dia Instruments), the generated gas is absorbed in 30 ppm of hydrogen peroxide solution, and sulfur qualification is performed by an ion chromatograph Compact IC761 (manufactured by Metrohm). And quantification was performed.
  • Example 2 A resin solution into which a methacryl group was introduced was obtained in the same manner as in Example 1 except that toluene was used instead of diethylene glycol monoethyl ether acetate. 6 parts of acetic acid was added to the resulting solution and stirred at 40 ° C. for 10 minutes. Next, after washing three times with water, toluene was distilled off while substituting with 30 parts of diethylene glycol monoethyl ether acetate to obtain a resin solution into which a methacryl group was introduced. Further, this resin was reacted with 61 parts of tetrahydrophthalic anhydride (0.4 equivalent with respect to the alcoholic hydroxyl group) to obtain a curable resin solution having developability. The same evaluation as in Example 1 was performed, and the results are shown in Table 1.
  • Example 3 A SUS reaction apparatus equipped with a stirrer, a cooling pipe, a thermometer, and an air introduction pipe was reacted with a novolac-type cresol resin (trade name “Shonol CRG-951”) manufactured by Showa Polymer Co., Ltd. and propylene oxide.
  • a novolac-type cresol resin trade name “Shonol CRG-951” manufactured by Showa Polymer Co., Ltd. and propylene oxide.
  • Resin having an alcoholic hydroxyl group (hydroxyl group: 386 g / eq., Average addition of about 5.0 mol of alkylene oxide per equivalent of phenolic hydroxyl group) 386 parts, ethyl acrylate 500 parts, bispentadionato zinc (Zn (acac)) 2 ) 7 parts, 0.3 part of methylhydroquinone as a polymerization inhibitor was charged, and the reaction was carried out at 100 ° C. while introducing dried air (50 ml / min). After starting the reaction, the resulting ethanol was reacted for 5 hours while distilling out of the reaction system together with ethyl acrylate.
  • alcoholic hydroxyl group hydroxyl group: 386 g / eq., Average addition of about 5.0 mol of alkylene oxide per equivalent of phenolic hydroxyl group
  • Example 4 An alcohol made by reacting a novolac-type cresol resin (trade name “Shonol CRG-951”) manufactured by Showa Polymer Co., Ltd. with ethylene oxide in a SUS reactor equipped with a stirrer, a cooling pipe, a thermometer, and an air introduction pipe 164 parts of resin having a hydroxyl group (hydroxyl group: 164 g / eq., Average addition of about 1.0 mol of alkylene oxide per equivalent of phenolic hydroxyl group), 200 parts of ethyl acrylate, zinc bispentadionato (Zn (acac) 2 ) 5 parts, 0.3 part of methylhydroquinone as a polymerization inhibitor was charged, and the reaction was carried out at 115 ° C.
  • a novolac-type cresol resin trade name “Shonol CRG-951”
  • ethylene oxide ethylene oxide
  • SUS reactor equipped with a stirrer, a cooling pipe, a thermometer, and an air introduction
  • Example 6 ⁇ Comparative Example 6>
  • the reaction was carried out in the same manner except that bispentadionatocopper (Cu (acac) 2 ) was used instead of bispentadionatozinc.
  • Cu (acac) 2 bispentadionatocopper
  • the acrylic group was polymerized, and the reaction solution was in a slurry state. became.
  • Example 7 ⁇ Comparative Example 7>
  • the reaction was carried out in the same manner except that trispentadionatomanganese (Mn (acac) 3 ) was used instead of bispentadionatozinc.
  • Mn (acac) 3 trispentadionatomanganese
  • the acrylic group was polymerized, and the reaction solution was slurried. became.
  • Example 8 ⁇ Comparative Example 8>
  • the reaction was carried out in the same manner except that bispentadionatocobalt (Co (acac) 2 ) was used instead of bispentadionatozinc.
  • the acrylic group was polymerized, and the reaction solution was slurried. became.
  • Example 9 ⁇ Comparative Example 9>
  • the reaction was carried out in the same manner except that trispentadionate iron (Fe (acac) 3 ) was used instead of bispentadionatozinc.
  • Fe (acac) 3 trispentadionate iron
  • the acrylic group was polymerized, and the reaction solution was slurried. became.
  • Example 10 ⁇ Comparative Example 10>
  • the reaction was carried out in the same manner except that pentadionium lithium (Li (acac)) was used instead of bispentadionatozinc.
  • Li (acac) pentadionium lithium
  • bispentadionatozinc bispentadionatozinc
  • a curable resin composition was prepared by kneading with a three-roll mill according to the blending ratio shown in Table 2 using the photosensitive resins obtained from the above Examples and Comparative Examples.
  • the photosensitive resin composition is applied to a printed circuit board that has been degreased in advance by a screen printing method so that the dry film thickness is 30 to 40 ⁇ m, preliminarily dried at 80 ° C. for 20 minutes, then cooled to room temperature and dried.
  • a coating film was obtained.
  • a negative film having a resist pattern is adhered to the coating film, exposed to 350 mJ / cm 3 using an ultraviolet exposure device, and after removing the negative film, a spray pressure of 2.0 kgf / cm using a 1% sodium carbonate aqueous solution is used.
  • PCT resistance The cured film was treated for PCT resistance under conditions of 121 ° C. and saturated vapor pressure for 50 hours, and evaluated according to the following criteria. The results are shown in Table 2.
  • ⁇ The cured film does not blister, peel off or discolor.
  • ⁇ The cured film has some swelling, peeling, and discoloration.
  • X The cured film has blistering, peeling and discoloration.
  • composition examples 1 to 4 are solder resists even if a photosensitive resin produced by a commonly used SUS reaction apparatus is used without using a glass reaction apparatus. As a result, it was confirmed that the reliability was not lowered.

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  • Physics & Mathematics (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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  • Spectroscopy & Molecular Physics (AREA)
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Abstract

The purpose of the present invention is to provide a method for producing a photosensitive resin that has reduced chlorinity, contains fewer metal-corroding components and the like, and is excellent in terms of required properties such as adhesiveness of the cured film, in order to achieve a highly reliable printed circuit board. The method for producing this photosensitive composition is characterized by: introducing a carboxylic acid ester (c) containing a polymerizable unsaturated group to a resin (b) having an extended chain in which some or all of the phenolic hydroxyl groups in a resin (a) having two or more phenolic hydroxyl groups per molecule are extended by a (poly) oxyalkylene group having an alcoholic hydroxyl group on an end, while in the presence of a zinc or zirconium acetylacetonate complex (d), and in the range of 0.2-0.8 equivalents of the polymerizable unsaturated group per 1 equivalent of the alcoholic hydroxyl group in the resin (b); and by reacting the remaining alcoholic hydroxyl groups with a polybasic acid anhydride (e).

Description

感光性樹脂の製造方法及び感光性樹脂組成物Method for producing photosensitive resin and photosensitive resin composition
　本発明はフェノール性水酸基を有する樹脂のフェノール性水酸基を（ポリ）オキシアルキレン基で鎖延長した樹脂と重合性不飽和基含有カルボン酸エステルとのエステル交換反応により重合性不飽和基を、亜鉛またはジルコニウムのアセチルアセトン錯体の存在下で導入し、得られる反応生成物に多塩基酸無水物を反応させる感光性樹脂の製造方法、およびその樹脂を含む感光性樹脂組成物に関する。 In the present invention, a polymerizable unsaturated group is converted into zinc or zinc by a transesterification reaction between a resin in which a phenolic hydroxyl group of a resin having a phenolic hydroxyl group is chain-extended with a (poly) oxyalkylene group and a polymerizable unsaturated group-containing carboxylic acid ester. The present invention relates to a method for producing a photosensitive resin that is introduced in the presence of an acetylacetone complex of zirconium and reacts the resulting reaction product with a polybasic acid anhydride, and a photosensitive resin composition containing the resin.
　近年、プリント配線板は電子機器の小型化、軽量化、高性能化に伴い、その配線板の回線自体を被覆するソルダーレジストへの要求もますます高度となっている。例えば、ＢＧＡ（ボールグリッドアレイ）、ＣＳＰ（チップサイズパッケージ）等の半導体パッケージにおいて、高信頼性の点から特にＰＣＴ性や高温高湿下における安定した電気特性が必要である。しかし、このような厳しい条件下において、ノボラック型エポキシ化合物と不飽和モノカルボン酸との反応物に、飽和または不飽和多塩基酸無水物を反応させて得られる光感光性樹脂を用いた従来のソルダーレジストでは要求を満足させるには不十分である。そこで、特許文献１には強靭性と耐熱性を向上させたフェノール樹脂とアルキレンオキサイド類を用いたカルボキシル基含有感光性樹脂組成物が記載されている。 In recent years, with the miniaturization, weight reduction, and performance enhancement of electronic devices, the demand for solder resist that covers the circuit itself of the circuit boards has become increasingly sophisticated. For example, semiconductor packages such as BGA (ball grid array) and CSP (chip size package) require stable electrical characteristics particularly under PCT and high temperature and high humidity from the viewpoint of high reliability. However, under such severe conditions, a conventional photo-sensitive resin obtained by reacting a reaction product of a novolak-type epoxy compound and an unsaturated monocarboxylic acid with a saturated or unsaturated polybasic acid anhydride is used. Solder resist is not sufficient to satisfy the requirements. Therefore, Patent Document 1 describes a carboxyl group-containing photosensitive resin composition using a phenol resin and alkylene oxides having improved toughness and heat resistance.
　一方、ソルダーレジストとして高温高湿下における電気特性の安定化には、樹脂中の塩素などの含有量低減が必要である。エポキシ樹脂を原料とする感光性樹脂は、エポキシ樹脂の製造法に由来する塩素が多く含まれているが、前記のフェノール樹脂とアルキレンオキサイド類を用いた感光性樹脂では製造の過程で塩素を使用しないため、塩素含有量は極めて少ない。しかし、これらは不飽和モノカルボン酸を導入する際に強酸などの触媒を用いるために、ステンレスなど金属類への腐食性が高く、製造装置に使用できる材質の選択範囲を狭め、設備費の増加を招いていた。さらに腐食により生じた金属成分が樹脂中に混入すると、電気絶縁性などのソルダーレジストとしての信頼性に大きな悪影響を及ぼす。また、これらの強酸の触媒を用いた場合は、反応後に中和、水洗、または吸着処理をするなどの繁雑な触媒除去工程が必要であり、多量の廃棄物が発生する。さらに、中和洗浄を行っても触媒が残存し、樹脂の色相や酸価の経時変化、基板上の金属の腐食を起こしやすくする。特許文献２では不飽和基含有カルボン酸エステルを用いた重合性不飽和基の導入が記載されているが、そのエステル化触媒も強酸性化合物であり上記のような問題を解決するものではない。 On the other hand, in order to stabilize electrical characteristics under high temperature and high humidity as a solder resist, it is necessary to reduce the content of chlorine in the resin. The photosensitive resin made from epoxy resin contains a lot of chlorine derived from the manufacturing method of epoxy resin, but the photosensitive resin using phenol resin and alkylene oxides mentioned above uses chlorine in the manufacturing process. Therefore, the chlorine content is extremely low. However, these use catalysts such as strong acids when introducing unsaturated monocarboxylic acids, so they are highly corrosive to metals such as stainless steel, narrowing the range of materials that can be used in production equipment, and increasing equipment costs. Was invited. Furthermore, when metal components generated by corrosion are mixed in the resin, the reliability as a solder resist such as electrical insulation is greatly adversely affected. Further, when these strong acid catalysts are used, a complicated catalyst removal step such as neutralization, washing with water, or adsorption treatment is required after the reaction, and a large amount of waste is generated. Furthermore, even if neutralization washing is performed, the catalyst remains, and it is easy to cause a change in the hue and acid value of the resin with time and corrosion of the metal on the substrate. Patent Document 2 describes the introduction of a polymerizable unsaturated group using an unsaturated group-containing carboxylic acid ester, but its esterification catalyst is also a strongly acidic compound and does not solve the above-described problems.
　また、特許文献３では、（メタ）アクリル酸の低級アルキルエステルとジアルキルアミノアルコールを金属のアセチルアセトン錯体存在下で反応させて、特定の式で表されるアクリル系モノマーを製造する方法を開示し、このアクリル系モノマーは高分子凝集剤、導電加工剤等の材料として有用である旨開示している。 Patent Document 3 discloses a method for producing an acrylic monomer represented by a specific formula by reacting a lower alkyl ester of (meth) acrylic acid with a dialkylamino alcohol in the presence of a metal acetylacetone complex, It is disclosed that this acrylic monomer is useful as a material such as a polymer flocculant and a conductive processing agent.
特許第３９６４３２６号明細書Patent No. 3964326 特許第３９７４８７５号明細書Japanese Patent No. 3974875 特開平０１－１８０８６１号公報Japanese Patent Laid-Open No. 01-180861
　上記従来の技術の問題に鑑み、本発明の目的は、プリント配線基板の高信頼性を達成するために、塩素量や金属腐食成分などの含有量が低減され、かつその硬化膜の密着性、はんだ耐熱性、耐吸湿性、ＰＣＴ耐性、電気絶縁性等、その他の要求される特性に優れる感光性樹脂を製造する方法を提供することであり、また、この製造方法による感光性樹脂を含む感光性樹脂組成物を提供することである。 In view of the above problems of the conventional technology, the object of the present invention is to reduce the content of chlorine and metal corrosive components in order to achieve high reliability of the printed wiring board, and to adhere the cured film, It is to provide a method for producing a photosensitive resin excellent in other required characteristics such as solder heat resistance, moisture absorption resistance, PCT resistance, electrical insulation, etc., and a photosensitive resin containing a photosensitive resin by this production method. It is providing a functional resin composition.
発明を解決するための手段Means for Solving the Invention
　本発明者らは鋭意検討の結果、フェノール性水酸基を有する樹脂のフェノール性水酸基を（ポリ）オキシアルキレン基で鎖延長した樹脂と重合性不飽和基含有カルボン酸エステルとのエステル交換反応において、亜鉛またはジルコニウムのアセチルアセトン錯体が極めて優れた活性を有していることを見出し、上述の従来の課題を解決することができた。
　すなわち本発明は、
（１）１分子中に２個以上のフェノール性水酸基を有する樹脂（ａ）のフェノール性水酸基の一部または全部を末端にアルコール性水酸基を有する（ポリ）オキシアルキレン基で鎖延長した樹脂（ｂ）に、重合性不飽和基含有カルボン酸エステル（ｃ）を、亜鉛またはジルコニウムのアセチルアセトン錯体（ｄ）の存在下で、重合性不飽和基が樹脂（ｂ）のアルコール性水酸基１当量に対して０．２～０．８当量となる範囲で導入し、さらに残りのアルコール性水酸基に多塩基酸無水物（ｅ）を反応させることを特徴とする感光性樹脂の製造方法、
（２）前記重合性不飽和基含有カルボン酸エステル（ｃ）が（メタ）アクリル酸エステルである、（１）の感光性樹脂の製造方法。
（３）前記樹脂（ｂ）に残存するフェノール性水酸基の量が樹脂（ａ）のフェノール性水酸基１当量に対して０．２当量以下であることを特徴とする、（１）または（２）の感光性樹脂の製造方法、
（４）（１）～（３）のいずれかに記載の製造方法により得られた感光性樹脂、エポキシ樹脂、光重合開始剤、並びに重合性不飽和化合物および／または溶剤を含む、感光性樹脂組成物を提供するものである。 As a result of intensive studies, the present inventors have found that in the transesterification reaction between a resin in which a phenolic hydroxyl group of a resin having a phenolic hydroxyl group is chain-extended with a (poly) oxyalkylene group and a polymerizable unsaturated group-containing carboxylic acid ester, zinc Or it discovered that the acetylacetone complex of zirconium had the very outstanding activity, and was able to solve the above-mentioned conventional subject.
That is, the present invention
(1) Resin having a chain extended with a (poly) oxyalkylene group having an alcoholic hydroxyl group at a part or all of the phenolic hydroxyl group of a resin (a) having two or more phenolic hydroxyl groups in one molecule (b) The polymerizable unsaturated group-containing carboxylic acid ester (c) is added to 1 equivalent of the alcoholic hydroxyl group of the resin (b) in the presence of the acetylacetone complex (d) of zinc or zirconium. Introducing in the range of 0.2 to 0.8 equivalents, and further reacting the remaining alcoholic hydroxyl group with polybasic acid anhydride (e),
(2) The method for producing a photosensitive resin according to (1), wherein the polymerizable unsaturated group-containing carboxylic acid ester (c) is a (meth) acrylic acid ester.
(3) The amount of the phenolic hydroxyl group remaining in the resin (b) is 0.2 equivalent or less with respect to 1 equivalent of the phenolic hydroxyl group of the resin (a), (1) or (2) Manufacturing method of photosensitive resin,
(4) A photosensitive resin comprising a photosensitive resin, an epoxy resin, a photopolymerization initiator, and a polymerizable unsaturated compound and / or solvent obtained by the production method according to any one of (1) to (3) A composition is provided.
　本発明の製造方法により得られた感光性樹脂は、その硬化膜が密着性、はんだ耐熱性、ＰＣＴ耐性に優れるだけでなく、高温高湿下にて安定した電気特性を有する。また、この製造方法では使用する反応装置の材質に限定されず、繁雑な水洗等の触媒洗浄を行わなくてもよい等、製造プロセスも簡易化でき、効率的に目的の感光性樹脂を得ることができ、工業的に極めて有利である。 The photosensitive resin obtained by the production method of the present invention is not only excellent in adhesion, solder heat resistance and PCT resistance, but also has stable electrical characteristics at high temperature and high humidity. In addition, this manufacturing method is not limited to the material of the reaction apparatus used, and it is not necessary to perform catalyst cleaning such as complicated water washing, so that the manufacturing process can be simplified and the desired photosensitive resin can be obtained efficiently. This is very advantageous industrially.
　本発明の詳細を以下に説明する。
　本発明における前記樹脂（ｂ）は、一般的に１分子中に２個以上のフェノール性水酸基を有する樹脂（ａ）にアルキレンオキサイド等を触媒下で反応させる方法で、末端にアルコール性水酸基を有する（ポリ）オキシアルキレン基を導入することにより得ることができる。また、アルキレンオキサイドの代わりに環状カーボネートなどでも製造することができるが、これらに限定されるものではない。 Details of the present invention will be described below.
The resin (b) in the present invention is generally a method in which an alkylene oxide or the like is reacted with a resin (a) having two or more phenolic hydroxyl groups in one molecule under a catalyst, and has an alcoholic hydroxyl group at the terminal. It can be obtained by introducing a (poly) oxyalkylene group. Moreover, although it can manufacture also with a cyclic carbonate etc. instead of an alkylene oxide, it is not limited to these.
　本発明における１分子中に２個以上のフェノール性水酸基を有する樹脂（ａ）としては、フェノール類とケトンとの縮合物、フェノール類とアルデヒドの縮合物、フェノール類とフェノール性水酸基を有する芳香族アルデヒドとの縮合物、ポリ－ｐ－ヒドロキシスチレン、ナフトール型ノボラック樹脂、トリスフェノールメタン型樹脂等が挙げられるがこれらに限定されるものではない。該化合物における各置換基の置換位置も特に限定されず、置換可能な位置異性体はすべて本発明に使用可能である。これらは単独または２種以上を使用することができる。 In the present invention, the resin (a) having two or more phenolic hydroxyl groups in one molecule includes a condensate of phenols and ketones, a condensate of phenols and aldehydes, and an aromatic having phenols and phenolic hydroxyl groups. Examples include, but are not limited to, condensates with aldehydes, poly-p-hydroxystyrene, naphthol type novolac resins, trisphenol methane type resins, and the like. The substitution position of each substituent in the compound is not particularly limited, and all substitutable isomers that can be substituted can be used in the present invention. These may be used alone or in combination of two or more.
　本発明における末端にアルコール性水酸基を有する（ポリ）オキシアルキレン基としては、オキシアルキレン単位の炭素数が２～６であることが好ましく、その炭化水素基としては、エチレン、プロピレン、ブチレン、ペンチレン、ヘキシレン、メチルプロピレン、プロピルエチレン等の直鎖状又は分岐状のアルキレン基が挙げられるが、これらに限定されるものではない。 In the present invention, the (poly) oxyalkylene group having an alcoholic hydroxyl group at the terminal preferably has 2 to 6 carbon atoms in the oxyalkylene unit. Examples of the hydrocarbon group include ethylene, propylene, butylene, pentylene, Examples include, but are not limited to, linear or branched alkylene groups such as hexylene, methylpropylene, and propylethylene.
　前記（ポリ）オキシアルキレン基は、前記樹脂（ａ）のフェノール性水酸基の一部または全部から鎖延長しており、樹脂（ｂ）において（ポリ）オキシアルキレン基が付加していない残存のフェノール性水酸基は前記樹脂（ａ）のフェノール性水酸基に対して０．２当量以下であることが好ましい。残存のフェノール性水酸基が前記樹脂（ａ）に対して０．２当量より多いと前記重合性不飽和基含有カルボン酸エステル（ｃ）との反応性が悪くなり、重合性不飽和基の導入量が低くなる恐れがある。 The (poly) oxyalkylene group is chain-extended from part or all of the phenolic hydroxyl group of the resin (a), and the residual phenolic group to which no (poly) oxyalkylene group is added in the resin (b) It is preferable that a hydroxyl group is 0.2 equivalent or less with respect to the phenolic hydroxyl group of the said resin (a). When the residual phenolic hydroxyl group is more than 0.2 equivalents relative to the resin (a), the reactivity with the polymerizable unsaturated group-containing carboxylic acid ester (c) is deteriorated, and the amount of polymerizable unsaturated groups introduced is reduced. May be low.
　前記オキシアルキレン単位の繰り返しは１～１０であることが好ましい。オキシアルキレン単位の繰り返しが１未満の場合、本発明の感光性樹脂において、光硬化性が乏しくなる恐れがある。また、オキシアルキレン単位の繰り返しが１０より多い場合、耐熱性の低下や光硬化性及び熱硬化性が乏しくなる恐れがある。 The number of repeating oxyalkylene units is preferably 1-10. When the number of repeating oxyalkylene units is less than 1, the photocurability of the photosensitive resin of the present invention may be poor. Further, when the number of repeating oxyalkylene units is more than 10, there is a fear that the heat resistance is lowered and the photocurability and the thermosetting property are poor.
　前記樹脂（ｂ）に重合性不飽和基含有カルボン酸エステル（ｃ）を触媒（ｄ）存在下でエステル交換反応により反応させることで、樹脂（ｂ）に重合性不飽和基を導入することができる。本発明における重合性不飽和基含有カルボン酸エステル（ｃ）としては、（メタ）アクリル酸エステルが好ましく、具体的には、アクリル酸メチル、アクリル酸エチル、アクリル酸プロピル、アクリル酸イソプロピル、アクリル酸ブチル、アクリル酸イソブチル、アクリル酸ペンチル、アクリル酸イソペンチル、アクリル酸ヘキシル、アクリル酸シクロヘキシル、アクリル酸オクチル、アクリル酸２－エチルーヘキシル、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸プロピル、メタクリル酸イソプロピル、メタクリル酸ブチル、メタクリル酸イソブチル、メタクリル酸ペンチル、メタクリル酸イソペンチル、メタクリル酸ヘキシル、メタクリル酸シクロヘキシル、メタクリル酸オクチル、メタクリル酸２－エチルーヘキシルなどが挙げられるが、これらに限られるものではない。 A polymerizable unsaturated group can be introduced into the resin (b) by reacting the polymerizable unsaturated group-containing carboxylic acid ester (c) with the resin (b) in the presence of the catalyst (d) by a transesterification reaction. it can. The polymerizable unsaturated group-containing carboxylic acid ester (c) in the present invention is preferably a (meth) acrylic acid ester, specifically, methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, acrylic acid. Butyl, isobutyl acrylate, pentyl acrylate, isopentyl acrylate, hexyl acrylate, cyclohexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, Butyl methacrylate, isobutyl methacrylate, pentyl methacrylate, isopentyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, etc. Including but not limited to these.
　重合性不飽和基の導入量は、前記樹脂（ｂ）のアルコール性水酸基１当量に対して、０．２～０．８当量（例えば、（メタ）アクリル酸エステルの場合は樹脂（ｂ）のアルコール性水酸基１モルに対して、０．２～０．８モル）が好ましく、更には０．４～０．６当量がより好ましい。重合性不飽和基の導入量が０．２当量未満の場合には、硬化性が不十分となり、ファインパターンが得られず、硬化塗膜の可とう性も得られにくく硬化時間も長くなり好ましくない。重合性不飽和基の導入量が０．８当量より大きい場合には、多塩基酸無水物と反応するアルコール性水酸基が少なくなるため、アルカリ現像性が悪くなる。 The amount of the polymerizable unsaturated group introduced is 0.2 to 0.8 equivalents relative to 1 equivalent of the alcoholic hydroxyl group of the resin (b) (for example, in the case of (meth) acrylic acid ester, the resin (b) 0.2 to 0.8 mol) is preferable with respect to 1 mol of alcoholic hydroxyl group, and more preferably 0.4 to 0.6 equivalent. When the introduction amount of the polymerizable unsaturated group is less than 0.2 equivalent, the curability is insufficient, the fine pattern cannot be obtained, the flexibility of the cured coating film is difficult to obtain, and the curing time is preferably increased. Absent. When the introduction amount of the polymerizable unsaturated group is larger than 0.8 equivalent, since the alcoholic hydroxyl group that reacts with the polybasic acid anhydride decreases, the alkali developability deteriorates.
　本発明で使用されるエステル交換の触媒（ｄ）としては、亜鉛、ジルコニウムのアセチルアセトン錯体を用いる。具体的にはビスペンタジオナト亜鉛（Ｚｎ（ａｃａｃ）2）、テトラキスペンタジオナトジルコニウム（Ｚｒ（ａｃａｃ）4））が挙げられる。これら触媒は無水物でも含水和物でもよく、市販のものがそのまま使用できる。その使用量は前記（ｂ）１００質量部に対して０．１～１０質量部が好ましい。触媒は全量を一度に仕込んでも良いが、数回に分けて加えても良い。触媒量が０．１質量部未満だと反応が進行しにくく、１０質量部より多く使用しても特に利点はない。 As the transesterification catalyst (d) used in the present invention, an acetylacetone complex of zinc and zirconium is used. Specific examples thereof include bispentadionato zinc (Zn (acac) 2 ) and tetrakispentadionato zirconium (Zr (acac) 4 )). These catalysts may be anhydrous or hydrated, and commercially available ones can be used as they are. The amount used is preferably 0.1 to 10 parts by mass per 100 parts by mass of (b). The catalyst may be charged all at once, but may be added in several batches. When the amount of catalyst is less than 0.1 parts by mass, the reaction does not proceed easily, and there is no particular advantage even if the amount exceeds 10 parts by mass.
　反応温度は５０～１５０℃、好ましくは８０～１３０℃であり、反応時間は使用する原料の種類と量、圧力、温度、触媒量等によって変わるが通常１～１０時間である。 The reaction temperature is 50 to 150 ° C., preferably 80 to 130 ° C., and the reaction time is usually 1 to 10 hours, although it varies depending on the type and amount of raw materials used, pressure, temperature, catalyst amount and the like.
　反応は無溶媒下または溶媒存在下に行うことができる。溶媒存在下に反応を行う場合、使用できる溶媒の種類としては、原料の不飽和基含有カルボン酸エステル、触媒及び反応生成物に対し不活性なものであれば、特に限定されるものでなく例えば、ベンゼン、トルエン、キシレン等の芳香族炭化水素類、ｎ－ヘキサン、ｎ－ヘプタン、シクロヘキサン等の脂肪族また脂環式炭化水素類、ジオキサン、ジイソプロピルエ－テル、テトラヒドロフラン等のエ－テル類、アセトニトリル、プロピオニトリル等のニトリル類等が挙げられる。特に、副生するアルコ－ルを共沸により反応系外に除去できる溶媒の使用が好ましく、具体的には前記芳香族炭化水素類、脂肪族または脂環式炭化水素類系の溶媒が好適である。また、用いる重合性不飽和基含有カルボン酸エステルの沸点によっては、重合性不飽和基含有カルボン酸エステルを副生するアルコ－ルとの共沸剤として利用し、アルコ－ルの留去をより速やかにすることもできる。 The reaction can be performed without solvent or in the presence of a solvent. When the reaction is carried out in the presence of a solvent, the type of solvent that can be used is not particularly limited as long as it is inert to the unsaturated group-containing carboxylic acid ester, catalyst, and reaction product of the raw material. Aromatic hydrocarbons such as benzene, toluene and xylene, aliphatic and alicyclic hydrocarbons such as n-hexane, n-heptane and cyclohexane, ethers such as dioxane, diisopropyl ether and tetrahydrofuran, Examples thereof include nitriles such as acetonitrile and propionitrile. In particular, it is preferable to use a solvent that can remove by-produced alcohol out of the reaction system by azeotropy, and specifically, the aromatic hydrocarbon, aliphatic or alicyclic hydrocarbon-based solvent is preferable. is there. Further, depending on the boiling point of the polymerizable unsaturated group-containing carboxylic acid ester to be used, the polymerizable unsaturated group-containing carboxylic acid ester is used as an azeotropic agent with the alcohol as a by-product to further distill off the alcohol. It can also be done quickly.
　原料である重合性不飽和基含有カルボン酸エステルは重合性を有するため、ハイドロキノン、ハイドロキノンモノメチルエ－テル、フェノチアジンなどの公知の重合禁止剤を使用することができる。また、重合禁止剤として酸素分子を用いることも有効である。この場合、空気を反応液内に送り込み副生するアルコ－ルを同伴させる方法が好ましい。 Since the raw material polymerizable unsaturated group-containing carboxylic acid ester has polymerizability, a known polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, phenothiazine or the like can be used. It is also effective to use oxygen molecules as a polymerization inhibitor. In this case, a method in which air is sent into the reaction solution and accompanied by by-produced alcohol is preferable.
　本発明では反応中にエステル化率を測定し、任意のエステル化率で反応を止めることで、エステル化率を制御することができる。つまり、反応中に樹脂をサンプリングし、エステル基や水酸基の量をＮＭＲやＩＲで測定し、目的のエステル化率になった時点で酢酸やアクリル酸などのカルボン酸類を加えることにより触媒の活性を抑えることができ、エステル化交換反応を止めることで、重合性不飽和基の導入量を制御することができる。 In the present invention, the esterification rate can be controlled by measuring the esterification rate during the reaction and stopping the reaction at an arbitrary esterification rate. In other words, the resin is sampled during the reaction, the amount of ester groups and hydroxyl groups is measured by NMR or IR, and the activity of the catalyst is increased by adding carboxylic acids such as acetic acid and acrylic acid when the desired esterification rate is reached. The amount of the polymerizable unsaturated group introduced can be controlled by stopping the esterification exchange reaction.
　本発明において、重合性不飽和基を導入後、必要に応じて触媒を取り除くために水洗などの洗浄を行っても良い。その際に、触媒を洗浄水に溶けやすくするために、製造装置を腐食するなどの影響がない程度に酢酸、アクリル酸、ＭｅＯＨなどの添加剤を加えても良い。 In the present invention, after introducing the polymerizable unsaturated group, washing with water or the like may be performed as necessary to remove the catalyst. At that time, an additive such as acetic acid, acrylic acid, or MeOH may be added to such an extent that the catalyst is easily dissolved in the washing water without causing an influence such as corrosion of the production apparatus.
　本発明において、樹脂（ｂ）と重合性不飽和基含有カルボン酸エステル（ｃ）の反応物である硬化性樹脂と多塩基酸無水物（ｅ）とを反応させ、アルカリ水溶液での現像性を示すカルボキシル基含有硬化性樹脂を得ることができる。 In the present invention, the curable resin, which is a reaction product of the resin (b) and the polymerizable unsaturated group-containing carboxylic acid ester (c), is reacted with the polybasic acid anhydride (e) to improve the developability in an aqueous alkali solution. The carboxyl group-containing curable resin shown can be obtained.
　使用できる多塩基酸無水物（ｅ）としては、無水マレイン酸、無水コハク酸、無水イタコン酸、無水フタル酸、テトラハイドロ無水フタル酸、ヘキサハイドロ無水フタル酸、エンドメチレンテトラハイドロ無水フタル酸、メチルテトラハイドロ無水フタル酸、無水クロレンド酸等の２塩基酸無水物、無水トリメリット酸、無水ピロメリット酸、ベンゾフェノンテトラカルボン酸無水物、ビフェニルテトラカルボン酸無水物等の多塩基酸無水物が挙げられ、とくにテトラヒドロ無水フタル酸、無水コハク酸、ヘキサハイドロ無水フタル酸の使用が好ましい。多塩基酸無水物（ｅ）の反応量は、樹脂中の残存アルコール性水酸基１当量に対して、多塩基酸無水物を０．１～１．０当量（例えば、テトラヒドロ無水フタル酸、無水コハク酸、ヘキサハイドロ無水フタル酸などの２塩基酸無水物の場合は、樹脂中の残存アルコール性水酸基１モルに対して、０．１～１．０モル）、好ましくは０．２～０．８当量用いるのがよい。多塩基酸無水物の付加量が０．１当量未満であると十分なアルカリ現像性が得られず、１．０当量を超えると、硬化塗膜の電気特性が低下してしまうおそれがある。 Usable polybasic acid anhydrides (e) include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methyl Examples include dibasic acid anhydrides such as tetrahydrophthalic anhydride and chlorendic anhydride, polybasic acid anhydrides such as trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, and biphenyltetracarboxylic anhydride. In particular, tetrahydrophthalic anhydride, succinic anhydride, and hexahydrophthalic anhydride are preferably used. The reaction amount of the polybasic acid anhydride (e) is 0.1 to 1.0 equivalent of polybasic acid anhydride (for example, tetrahydrophthalic anhydride, succinic anhydride) with respect to 1 equivalent of residual alcoholic hydroxyl group in the resin. In the case of a dibasic acid anhydride such as acid or hexahydrophthalic anhydride, 0.1 to 1.0 mol), preferably 0.2 to 0.8 mol, per 1 mol of the remaining alcoholic hydroxyl group in the resin. Equivalent amounts should be used. If the addition amount of the polybasic acid anhydride is less than 0.1 equivalent, sufficient alkali developability cannot be obtained, and if it exceeds 1.0 equivalent, the electric properties of the cured coating film may be deteriorated.
　本発明の製造方法で得られる感光性樹脂はエポキシ樹脂、光重合開始剤、並びに重合性不飽和化合物および／または溶剤を含む感光性樹脂組成物を提供し、レジストインキなどの用途で使用することができる。 The photosensitive resin obtained by the production method of the present invention provides a photosensitive resin composition containing an epoxy resin, a photopolymerization initiator, and a polymerizable unsaturated compound and / or a solvent, and is used for applications such as resist inks. Can do.
　エポキシ樹脂としては、例えば１分子中にエポキシ基を２個以上有するものであって、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、水添ビスフェノールＡ型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、ジシクロペンタジエン－フェノールノボラック型エポキシ樹脂、フェノール－クレゾールノボラック共縮合型エポキシ樹脂、ビスフェノールＡノボラック型エポキシ樹脂、ビスフェノールＦノボラック型エポキシ樹脂あるいはそれらのハロゲン化エポキシ化合物、トリフェニロールメタン型エポキシ樹脂、アルキル置換トリフェニロールメタン型エポキシ樹脂、テトラフェニロールエタン型エポキシ樹脂等の多官能フェノールにエピクロルヒドリンを反応させて得られるエポキシ樹脂、多官能ヒドロキシナフタレン類エピクロルヒドリンを反応させて得られるエポキシ樹脂、シリコーン変性エポキシ樹脂、ε－カプロラクトン変性エポキシ樹脂、エピクロルヒドリンと一級または二級アミンとの反応によって得られるグリシジルアミン型エポキシ樹脂、トリグリシジルイソシアネート等の複素環式エポキシ樹脂等が挙げられる。これらエポキシ樹脂の１種もしくは２種以上を併用してもよい。 Examples of the epoxy resin include those having two or more epoxy groups in one molecule, and are bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, phenol novolac type epoxy resin, cresol novolak. Type epoxy resin, dicyclopentadiene-phenol novolac type epoxy resin, phenol-cresol novolac co-condensation type epoxy resin, bisphenol A novolac type epoxy resin, bisphenol F novolac type epoxy resin or their halogenated epoxy compounds, triphenylol methane type Epichlorohydrin is reacted with polyfunctional phenol such as epoxy resin, alkyl-substituted triphenylol methane type epoxy resin, tetraphenylol ethane type epoxy resin, etc. An epoxy resin obtained by reacting a polyfunctional hydroxynaphthalene epichlorohydrin, a silicone-modified epoxy resin, an ε-caprolactone-modified epoxy resin, a glycidylamine-type epoxy resin obtained by reaction of epichlorohydrin with a primary or secondary amine, Examples include heterocyclic epoxy resins such as triglycidyl isocyanate. One or two or more of these epoxy resins may be used in combination.
　これらエポキシ樹脂の使用量は、本発明の製造法で得られる感光性樹脂１００質量部に対して、３～１００質量部、好ましくは、６～７５質量部である。エポキシ樹脂が３質量部未満では、本発明の製造方法で得られる感光性樹脂中のカルボキシル基が実質的に反応する量に満たされないため、耐水性、耐アルカリ性、電気特性が低下してしまい好ましくない。一方、１００質量部を超える場合では、未反応のエポキシ基を有する線状重合体が生成するため、耐熱性、耐溶剤性が不十分となり、何れも好ましくない。 These epoxy resins are used in an amount of 3 to 100 parts by weight, preferably 6 to 75 parts by weight, based on 100 parts by weight of the photosensitive resin obtained by the production method of the present invention. When the epoxy resin is less than 3 parts by mass, the carboxyl group in the photosensitive resin obtained by the production method of the present invention is not satisfied with the amount that substantially reacts, so that the water resistance, alkali resistance, and electrical characteristics are deteriorated. Absent. On the other hand, when the amount exceeds 100 parts by mass, a linear polymer having an unreacted epoxy group is generated, so that the heat resistance and the solvent resistance become insufficient.
　次に、光重合開始剤としては、ベンゾイン、ベンゾインメチルエーテル、ベンゾインイソプロピルエーテル、ベンゾインイソブチルエーテル等のベンゾインおよびその誘導体、ベンジルジメチルケタール等のベンジルケタールおよびその誘導体、アセトフェノン、２，２－ジメトキシ－２－フェニルアセトフェノン、２，２－ジエトキシ－２－フェニルアセトフェノン、１，１－ジクロルアセトフェノン、１－ヒドロキシシクロヘキシルフェニルケトン、２－メチル－１－(４－メチルチオフィル) －２－モルフォリノプロパン－１－オン等のアセトフェノンおよびその誘導体、２－メチルアントラキノン、２－クロロアントラキノン、２－エチルアントラキノン、２－ｔ－ブチルアントラキノン等のアントラキノンおよびその誘導体、チオキサントン、２，４－ジメチルチオキサントン、２－クロロチオキサン等のチオキサントンおよびその誘導体、ベンゾフェノン、Ｎ，Ｎ－ジメチルアミノベンゾフェノン等のベンゾフェノンおよびその誘導体が挙げられ、これら光重合開始剤の１種もしくは２種以上を併用してもよい。 Next, as photopolymerization initiators, benzoin and its derivatives such as benzoin, benzoin methyl ether, benzoin isopropyl ether and benzoin isobutyl ether, benzyl ketal and its derivatives such as benzyldimethyl ketal, acetophenone, 2,2-dimethoxy-2 -Phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4-methylthiophyl) -2-morpholinopropane-1 Acetophenone and its derivatives such as -one, anthraquinone and its derivatives such as 2-methylanthraquinone, 2-chloroanthraquinone, 2-ethylanthraquinone and 2-t-butylanthraquinone, thio Examples thereof include thioxanthone such as xanthone, 2,4-dimethylthioxanthone and 2-chlorothioxan and derivatives thereof, and benzophenone and derivatives thereof such as benzophenone and N, N-dimethylaminobenzophenone. One or two of these photopolymerization initiators More than one species may be used in combination.
　さらに必要に応じて、各種のアミン化合物をこれら光重合開始剤と併用することにより、光重合開始効果が促進されることが公知であり、本発明においても、組み合わせて使用することができる。光重合開始剤の使用量は、本発明の製造法で得られる感光性樹脂１００質量部に対して、０．１～２０質量部、好ましくは１～１０質量部である。重合性不飽和化合物および／または溶剤は、活性エネルギー光線に対する硬化性および／または感光性樹脂組成物をレジストインキとして使用する場合の塗工性を向上させる目的で使用するものである。重合性不飽和化合物としては、活性エネルギー光線硬化性のあるモノマー類が好ましく、２－ヒドロキシエチルアクリレート、２－ヒドロキシプロピルアクリレート、Ｎ－ピロリドン、Ｎ－アクリロイルモルフォリン、Ｎ，Ｎ－ジメチルアクリルアミド、Ｎ，Ｎ－ジエチルアクリルアミド、Ｎ，Ｎ－ジメチルアミノエチルアクリレート、Ｎ，Ｎ－ジメチルアミノプロピルアクリレート、メトキシポリエチレングリコールアクリレート、エトキシポリエチレングリコールアクリレート、メラミンアクリレート、フェノキシエチルアクリレート、フェノキシプロピルアクリレート、エチレングリコールジアクリレート、ジプロピレングリコールジアクリレート、ポリジプロピレングリコールジアクリレート、トリメチロールプロパントリアクリレート、ペンタエリスリトールトリアクリレート、ペンタエリスリトールテトラアクリレート、ジペンタエリスリトールヘキサアクリレート、グリセリンジアクリレート、イソボロニルアクリレート、ジシクロペンテニルオキシエチルアクリレートおよびこれらに対応する各種メタクリレートが挙げられる。これら重合性不飽和化合物の１種もしくは２種以上を併用してもよい。 Further, it is known that the photopolymerization initiating effect is promoted by using various amine compounds in combination with these photopolymerization initiators as required, and they can be used in combination in the present invention. The amount of the photopolymerization initiator used is 0.1 to 20 parts by mass, preferably 1 to 10 parts by mass, with respect to 100 parts by mass of the photosensitive resin obtained by the production method of the present invention. The polymerizable unsaturated compound and / or the solvent is used for the purpose of improving the curability to active energy rays and / or the coating property when the photosensitive resin composition is used as a resist ink. The polymerizable unsaturated compound is preferably an active energy light curable monomer, such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, N-pyrrolidone, N-acryloylmorpholine, N, N-dimethylacrylamide, N , N-diethylacrylamide, N, N-dimethylaminoethyl acrylate, N, N-dimethylaminopropyl acrylate, methoxypolyethylene glycol acrylate, ethoxypolyethylene glycol acrylate, melamine acrylate, phenoxyethyl acrylate, phenoxypropyl acrylate, ethylene glycol diacrylate, Dipropylene glycol diacrylate, polydipropylene glycol diacrylate, trimethylolpropane triacrylate DOO, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, glycerol diacrylate isobornyl acrylate, dicyclopentenyl oxyethyl acrylate and the corresponding various methacrylates thereof. One or two or more of these polymerizable unsaturated compounds may be used in combination.
　一方、溶剤としては、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン類、トルエン、キシレン等の芳香族炭化水素、エチルセロソルブ、ブチルセロソルブ、カルビトール、ブチルカルビトール等のカルビトール類、酢酸エチル、酢酸ブチル、セロソルブアセテート、ブチルセロソルブアセテート、カルビトールアセテート等が挙げられる。これらの溶剤は１種もしくは２種以上を併用してもよい。重合性不飽和化合物または溶剤は、単独または２種類以上の混合物として用いられる。そして、重合性不飽和化合物および／または溶剤の使用量は、本発明の製造法で得られる感光性樹脂１００質量部に対して、１０～２００質量部、好ましくは２０～１５０質量部である。中でも重合性不飽和化合物の使用量が、１０質量部未満では、光感度が低すぎ、一方２００質量部を超えると感光性樹脂組成物をレジストインキとして使用する場合に粘度が低くなりすぎ、硬化塗膜としての耐性が不十分になる。 On the other hand, as solvents, ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene and xylene, carbitols such as ethyl cellosolve, butyl cellosolve, carbitol and butyl carbitol, ethyl acetate and butyl acetate , Cellosolve acetate, butyl cellosolve acetate, carbitol acetate and the like. These solvents may be used alone or in combination of two or more. The polymerizable unsaturated compound or solvent is used alone or as a mixture of two or more. The amount of the polymerizable unsaturated compound and / or solvent used is 10 to 200 parts by weight, preferably 20 to 150 parts by weight, based on 100 parts by weight of the photosensitive resin obtained by the production method of the present invention. Above all, when the amount of the polymerizable unsaturated compound used is less than 10 parts by mass, the photosensitivity is too low. On the other hand, when it exceeds 200 parts by mass, the viscosity becomes too low when the photosensitive resin composition is used as a resist ink. Resistance as a coating film becomes insufficient.
　この他、本発明の感光性樹脂組成物を液状レジストインキとして使用する場合には、さらに必要に応じて、シリカ、炭酸カルシウム、硫酸バリウム、クレー、タルク等の無機充填剤、フタロシアニングリーン、フタロシアニンブルー、酸化チタン、カーボンブラック等の着色顔料、消泡剤、レベリング剤等の各種添加剤の他、ハイドロキノン、レゾルシノール、カテコール、ピロガノール、ハイドロキノンモノメチルエーテル、ｔ－ブチルカテコール、フェノチアジン等の重合防止剤を使用してもよい。本発明の感光性樹脂組成物を硬化せしめるための照射光源としては、低圧水銀灯、中圧水銀灯、高圧水銀灯、キセノンランプ、メタルハライドランプ等が適当である。その他、レーザー光線も使用し得る。 In addition, when the photosensitive resin composition of the present invention is used as a liquid resist ink, if necessary, inorganic fillers such as silica, calcium carbonate, barium sulfate, clay, talc, phthalocyanine green, phthalocyanine blue In addition to color pigments such as titanium oxide and carbon black, various additives such as antifoaming agents and leveling agents, polymerization inhibitors such as hydroquinone, resorcinol, catechol, pyroganol, hydroquinone monomethyl ether, t-butylcatechol, and phenothiazine are used. May be. As the irradiation light source for curing the photosensitive resin composition of the present invention, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, a xenon lamp, a metal halide lamp and the like are suitable. In addition, a laser beam can also be used.
　以下に実施例および比較例を示して、本発明を具体的に説明する。なお部および％とあるのは、とくに断らない限り、全て質量基準である。 Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. All parts and percentages are based on mass unless otherwise specified.
＜実施例１＞
　撹拌機、冷却管、温度計、空気導入管を備えたＳＵＳ（ステンレス）製の反応装置に、昭和高分子株式会社製ノボラック型クレゾール樹脂（商品名「ショウノールＢＲＧ－５５６」）とエチレンオキシドを反応させたアルコール性水酸基を有する樹脂（水酸基：２３９ｇ／ｅｑ．、フェノール性水酸基１当量当りアルキレンオキシドが平均約３．０モル付加）２３９部、メタクリル酸メチル６００部、テトラキスペンタジオナトジルコニウム（Ｚｒ（ａｃａｃ）4）５部、重合禁止剤としてメチルハイドロキノン０．２部を仕込み、乾燥させた空気を導入（５０ｍｌ／ｍｉｎ）しながら１００℃で反応を行った。反応開始後、生成したメタノールをメタクリル酸メチルと共に反応系外に留出させながら７時間反応させた。ジエチレングリコールモノエチルエーテルアセテート３０部を加え、真空蒸留を行い、余分なメタクリル酸メチル、メタノールを除くことでメタクリル基を導入した樹脂溶液を得た。さらに、この樹脂をテトラヒドロ無水フタル酸６１部（アルコール性水酸基に対して０．４当量）と反応させ、現像性を有する硬化性樹脂溶液を得た。
　得られた樹脂溶液について以下に示す評価を実施した。結果を表１に示した。 <Example 1>
A reaction vessel made of SUS (stainless steel) equipped with a stirrer, cooling tube, thermometer, and air introduction tube reacts with Novolac-type cresol resin (trade name “Shornol BRG-556”) manufactured by Showa Polymer Co., Ltd. 239 parts of a resin having an alcoholic hydroxyl group (hydroxyl group: 239 g / eq., Average addition of about 3.0 mol of alkylene oxide per equivalent of phenolic hydroxyl group), 600 parts of methyl methacrylate, tetrakispentadionatozirconium (Zr ( acac) 4 ) 5) and 0.2 part of methylhydroquinone as a polymerization inhibitor were charged, and the reaction was carried out at 100 ° C. while introducing dried air (50 ml / min). After starting the reaction, the resulting methanol was reacted for 7 hours while distilling out of the reaction system together with methyl methacrylate. 30 parts of diethylene glycol monoethyl ether acetate was added, vacuum distillation was performed, and excess methyl methacrylate and methanol were removed to obtain a resin solution into which a methacryl group was introduced. Further, this resin was reacted with 61 parts of tetrahydrophthalic anhydride (0.4 equivalent with respect to the alcoholic hydroxyl group) to obtain a curable resin solution having developability.
The evaluation shown below was implemented about the obtained resin solution. The results are shown in Table 1.
＜評価項目と測定法＞
〔不飽和基含有カルボキシル基の導入量〕
　原料であるアルコール性水酸基を有する樹脂とそのアルコール性水酸基に対して１当量の重合性不飽和基含有カルボン酸エステルを混合した溶液を重クロロホルムに溶解させ、1Ｈ－ＮＭＲ（日本電子データム株式会社製、ＪＮＭ－ＬＡ３００）を用いて分析し、その時の原料であるアルコール性水酸基を有する樹脂由来の芳香環のピークと重合性不飽和基含有カルボン酸エステル由来の重合性不飽和基のピークの積分値の比率を導入率１００％とし、反応中又は反応終了後の樹脂の芳香環のピークと導入された重合性不飽和基のピークの積分値の比率を測定することで重合性不飽和基の導入量を算出した。 <Evaluation items and measurement methods>
[Introduction amount of unsaturated group-containing carboxyl group]
A solution prepared by mixing a resin having an alcoholic hydroxyl group as a raw material and one equivalent of a polymerizable unsaturated group-containing carboxylic acid ester with respect to the alcoholic hydroxyl group is dissolved in deuterated chloroform, and 1 H-NMR (JEOL Datum Co., Ltd.) JNM-LA300), and integration of the peak of the aromatic ring derived from the resin having an alcoholic hydroxyl group and the peak of the polymerizable unsaturated group derived from the polymerizable unsaturated group-containing carboxylic acid ester. The ratio of the value was set to 100%, and the ratio of the integrated value of the peak of the aromatic ring of the resin during the reaction or after completion of the reaction and the peak of the introduced polymerizable unsaturated group was measured to determine the ratio of the polymerizable unsaturated group. The amount introduced was calculated.
〔不純物の含有量〕
　得られた樹脂溶液を自動試料燃焼装置ＡＱＦ－１００（ダイアインスツルメンツ社製）によって燃焼させ、発生したガスを過酸化水素水３０ｐｐｍに吸収させてイオンクロマトグラフＣｏｍｐａｃｔＩＣ７６１（Ｍｅｔｒｏｈｍ社製）によって、硫黄の定性および定量を実施した。 [Content of impurities]
The obtained resin solution is combusted by an automatic sample combustion apparatus AQF-100 (manufactured by Dia Instruments), the generated gas is absorbed in 30 ppm of hydrogen peroxide solution, and sulfur qualification is performed by an ion chromatograph Compact IC761 (manufactured by Metrohm). And quantification was performed.
＜実施例２＞
　実施例１においてジエチレングリコールモノエチルエーテルアセテートの代わりにトルエンを用いた以外は同様にしてメタクリル基を導入した樹脂溶液を得た。得られた溶液に酢酸６部を加え、４０℃で１０分撹拌した。次に、水洗を３回行った後にトルエンをジエチレングリコールモノエチルエーテルアセテート３０部で置換しつつ留去し、メタクリル基を導入した樹脂溶液を得た。さらに、この樹脂をテトラヒドロ無水フタル酸６１部（アルコール性水酸基に対して０．４当量）と反応させ、現像性を有する硬化性樹脂溶液を得た。実施例１と同様の評価を行い、結果を表１に示した。 <Example 2>
A resin solution into which a methacryl group was introduced was obtained in the same manner as in Example 1 except that toluene was used instead of diethylene glycol monoethyl ether acetate. 6 parts of acetic acid was added to the resulting solution and stirred at 40 ° C. for 10 minutes. Next, after washing three times with water, toluene was distilled off while substituting with 30 parts of diethylene glycol monoethyl ether acetate to obtain a resin solution into which a methacryl group was introduced. Further, this resin was reacted with 61 parts of tetrahydrophthalic anhydride (0.4 equivalent with respect to the alcoholic hydroxyl group) to obtain a curable resin solution having developability. The same evaluation as in Example 1 was performed, and the results are shown in Table 1.
＜実施例３＞
　撹拌機、冷却管、温度計、空気導入管を備えたＳＵＳ製の反応装置に、昭和高分子株式会社製ノボラック型クレゾール樹脂（商品名「ショウノールＣＲＧ－９５１」）とプロピレンオキシドを反応させたアルコール性水酸基を有する樹脂（水酸基：３８６ｇ／ｅｑ．、フェノール性水酸基１当量当りアルキレンオキシドが平均約５．０モル付加）３８６部、アクリル酸エチル５００部、ビスペンタジオナト亜鉛（Ｚｎ（ａｃａｃ）2）７部、重合禁止剤としてメチルハイドロキノン０．３部を仕込み、乾燥させた空気を導入（５０ｍｌ／ｍｉｎ）しながら１００℃で反応を行った。反応開始後、生成したエタノールをアクリル酸エチルと共に反応系外に留出させながら５時間反応させた。ジエチレングリコールモノエチルエーテルアセテート５０部を加え、真空蒸留を行い、余分なアクリル酸エチル、エタノールを除くことでアクリル基を導入した樹脂溶液を得た。さらに、この樹脂をテトラヒドロ無水フタル酸９１部（アルコール性水酸基に対して０．６当量）と反応させ、現像性を有する硬化性樹脂溶液を得た。実施例１と同様の評価を行い、結果を表１に示した。 <Example 3>
A SUS reaction apparatus equipped with a stirrer, a cooling pipe, a thermometer, and an air introduction pipe was reacted with a novolac-type cresol resin (trade name “Shonol CRG-951”) manufactured by Showa Polymer Co., Ltd. and propylene oxide. Resin having an alcoholic hydroxyl group (hydroxyl group: 386 g / eq., Average addition of about 5.0 mol of alkylene oxide per equivalent of phenolic hydroxyl group) 386 parts, ethyl acrylate 500 parts, bispentadionato zinc (Zn (acac)) 2 ) 7 parts, 0.3 part of methylhydroquinone as a polymerization inhibitor was charged, and the reaction was carried out at 100 ° C. while introducing dried air (50 ml / min). After starting the reaction, the resulting ethanol was reacted for 5 hours while distilling out of the reaction system together with ethyl acrylate. 50 parts of diethylene glycol monoethyl ether acetate was added, vacuum distillation was performed, and excess ethyl acrylate and ethanol were removed to obtain a resin solution into which an acrylic group was introduced. Further, this resin was reacted with 91 parts of tetrahydrophthalic anhydride (0.6 equivalent with respect to the alcoholic hydroxyl group) to obtain a curable resin solution having developability. The same evaluation as in Example 1 was performed, and the results are shown in Table 1.
＜実施例４＞
　撹拌機、冷却管、温度計、空気導入管を備えたＳＵＳ製の反応装置に、昭和高分子株式会社製ノボラック型クレゾール樹脂（商品名「ショウノールＣＲＧ－９５１」）とエチレンオキシドを反応させたアルコール性水酸基を有する樹脂（水酸基：１６４ｇ／ｅｑ．、フェノール性水酸基１ 当量当りアルキレンオキシドが平均約１．０モル付加）１６４部、アクリル酸エチル２００部、ビスペンタジオナト亜鉛（Ｚｎ（ａｃａｃ）2）５部、重合禁止剤としてメチルハイドロキノン０．３部を仕込み、乾燥させた空気を導入（５０ｍｌ／ｍｉｎ）しながら１１５℃で反応を行った。反応開始後、生成したエタノールをアクリル酸エチルと共に反応系外に留出させながら５時間反応させた。ジエチレングリコールモノエチルエーテルアセテート１２０部を加え、真空蒸留を行い、余分なアクリル酸エチル、エタノールを除くことでアクリル基を導入した樹脂溶液を得た。さらに、この樹脂をテトラヒドロ無水フタル酸６１部（アルコール性水酸基に対して０．４当量）と反応させ、現像性を有する硬化性樹脂溶液を得た。実施例１と同様の評価を行い、結果を表１に示した。 <Example 4>
An alcohol made by reacting a novolac-type cresol resin (trade name “Shonol CRG-951”) manufactured by Showa Polymer Co., Ltd. with ethylene oxide in a SUS reactor equipped with a stirrer, a cooling pipe, a thermometer, and an air introduction pipe 164 parts of resin having a hydroxyl group (hydroxyl group: 164 g / eq., Average addition of about 1.0 mol of alkylene oxide per equivalent of phenolic hydroxyl group), 200 parts of ethyl acrylate, zinc bispentadionato (Zn (acac) 2 ) 5 parts, 0.3 part of methylhydroquinone as a polymerization inhibitor was charged, and the reaction was carried out at 115 ° C. while introducing dried air (50 ml / min). After starting the reaction, the resulting ethanol was reacted for 5 hours while distilling out of the reaction system together with ethyl acrylate. 120 parts of diethylene glycol monoethyl ether acetate was added, vacuum distillation was performed, and excess ethyl acrylate and ethanol were removed to obtain a resin solution into which an acrylic group was introduced. Further, this resin was reacted with 61 parts of tetrahydrophthalic anhydride (0.4 equivalent with respect to the alcoholic hydroxyl group) to obtain a curable resin solution having developability. The same evaluation as in Example 1 was performed, and the results are shown in Table 1.
＜比較例１＞
　撹拌機、冷却管、温度計、空気導入管を備えたガラス製の反応装置に、昭和高分子株式会社製ノボラック型クレゾール樹脂（ 商品名「ショウノールＣＲＧ－９５１」）とエチレンオキシドを反応させたアルコール性水酸基を有する樹脂（水酸基：１６４ｇ／ｅｑ．、フェノール性水酸基１当量当りアルキレンオキシドが平均約１．０モル付加）１６４部、アクリル酸４３部、パラトルエンスルホン酸２．７部、トルエン１５０部、重合禁止剤としてメチルハイドロキノン０．１部を仕込み、乾燥させた空気を導入（５０ｍｌ／ｍｉｎ）しながら１１０℃で反応を行った。反応開始後、生成した水をトルエンと共に反応系外に留出させながら１０時間反応させた。その後、室温まで冷却し、得られた反応溶液を１５％水酸化ナトリウム水溶液で中和し、次いで水洗した。その後、トルエンをジエチレングリコールモノエチルエーテルアセテート１２０部で置換しつつ留去し、感光性樹脂溶液を得た。
　次に、トリフェニルホスフィン０．３部、テトラヒドロ無水フタル酸５５部（アルコール性水酸基に対して０．４当量）を加え、乾燥させた空気を導入（５０ｍｌ／ｍｉｎ）しながら、１１０℃で６時間反応させ、現像性を有する感光性樹脂溶液を得た。得られた感光性樹脂溶液の硫黄量について測定した結果を表１に示した。 <Comparative Example 1>
Alcohol in which novolac-type cresol resin (trade name “Shonol CRG-951”) manufactured by Showa Polymer Co., Ltd. was reacted with ethylene oxide in a glass reactor equipped with a stirrer, cooling tube, thermometer, and air introduction tube Resin having a hydroxyl group (hydroxyl group: 164 g / eq., Average addition of about 1.0 mol of alkylene oxide per equivalent of phenolic hydroxyl group) 164 parts, acrylic acid 43 parts, paratoluenesulfonic acid 2.7 parts, toluene 150 parts Then, 0.1 part of methylhydroquinone was charged as a polymerization inhibitor and reacted at 110 ° C. while introducing dried air (50 ml / min). After starting the reaction, the resulting water was reacted for 10 hours while distilling out of the reaction system together with toluene. Thereafter, the mixture was cooled to room temperature, and the resulting reaction solution was neutralized with a 15% aqueous sodium hydroxide solution and then washed with water. Then, toluene was distilled off while substituting with 120 parts of diethylene glycol monoethyl ether acetate to obtain a photosensitive resin solution.
Next, 0.3 parts of triphenylphosphine and 55 parts of tetrahydrophthalic anhydride (0.4 equivalents with respect to the alcoholic hydroxyl group) were added, and 6 hours at 110 ° C. while introducing dried air (50 ml / min). The reaction was carried out for a time to obtain a photosensitive resin solution having developability. Table 1 shows the results of measuring the amount of sulfur in the obtained photosensitive resin solution.
＜比較例２＞
　比較例１においてガラス製の反応装置の代わりにＳＵＳ製の反応装置を用いた以外は同様にして、現像性を有する硬化性樹脂溶液を得た。実施例１と同様の評価を行い、結果を表１に示した。 <Comparative Example 2>
A curable resin solution having developability was obtained in the same manner as in Comparative Example 1 except that a SUS reactor was used instead of the glass reactor. The same evaluation as in Example 1 was performed, and the results are shown in Table 1.
＜比較例３＞
　実施例４においてビスペンタジオナト亜鉛の代わりにテトライソプロポキシチタンを用いた以外は同様にして反応を行った。実施例１と同様の評価を行い、結果を表１に示した。 <Comparative Example 3>
The reaction was conducted in the same manner as in Example 4 except that tetraisopropoxytitanium was used instead of bispentadionatozinc. The same evaluation as in Example 1 was performed, and the results are shown in Table 1.
＜比較例４＞
　実施例４においてビスペンタジオナト亜鉛の代わりにビスペンタジオナトカルシウム（Ｃａ（ａｃａｃ）2）を用いた以外は同様にして反応を行った。実施例１と同様の評価を行い、結果を表１に示した。 <Comparative example 4>
The reaction was conducted in the same manner as in Example 4 except that bispentadionatocalcium (Ca (acac) 2 ) was used instead of bispentadionatozinc. The same evaluation as in Example 1 was performed, and the results are shown in Table 1.
＜比較例５＞
　実施例４においてビスペンタジオナト亜鉛の代わりにトリスペンタジオナトアルミニウム（Ａｌ（ａｃａｃ）3）を用いた以外は同様にして反応を行った。実施例１と同様の評価を行い、結果を表１に示した。 <Comparative Example 5>
The reaction was conducted in the same manner as in Example 4 except that trispentadionato aluminum (Al (acac) 3 ) was used instead of bispentadionato zinc. The same evaluation as in Example 1 was performed, and the results are shown in Table 1.
＜比較例６＞
　実施例４においてビスペンタジオナト亜鉛の代わりにビスペンタジオナト銅（Ｃｕ（ａｃａｃ）2）を用いた以外は同様にして反応を行ったところ、アクリル基が重合し、反応液はスラリー状になった。 <Comparative Example 6>
In Example 4, the reaction was carried out in the same manner except that bispentadionatocopper (Cu (acac) 2 ) was used instead of bispentadionatozinc. As a result, the acrylic group was polymerized, and the reaction solution was in a slurry state. became.
＜比較例７＞
　実施例４においてビスペンタジオナト亜鉛の代わりにトリスペンタジオナトマンガン（Ｍｎ（ａｃａｃ）3）を用いた以外は同様にして反応を行ったところ、アクリル基が重合し、反応液はスラリー状になった。 <Comparative Example 7>
In Example 4, the reaction was carried out in the same manner except that trispentadionatomanganese (Mn (acac) 3 ) was used instead of bispentadionatozinc. As a result, the acrylic group was polymerized, and the reaction solution was slurried. became.
＜比較例８＞
　実施例４においてビスペンタジオナト亜鉛の代わりにビスペンタジオナトコバルト（Ｃｏ（ａｃａｃ）2）を用いた以外は同様にして反応を行ったところ、アクリル基が重合し、反応液はスラリー状になった。 <Comparative Example 8>
In Example 4, the reaction was carried out in the same manner except that bispentadionatocobalt (Co (acac) 2 ) was used instead of bispentadionatozinc. As a result, the acrylic group was polymerized, and the reaction solution was slurried. became.
＜比較例９＞
　実施例４においてビスペンタジオナト亜鉛の代わりにトリスペンタジオナト鉄（Ｆｅ（ａｃａｃ）3）を用いた以外は同様にして反応を行ったところ、アクリル基が重合し、反応液はスラリー状になった。 <Comparative Example 9>
In Example 4, the reaction was carried out in the same manner except that trispentadionate iron (Fe (acac) 3 ) was used instead of bispentadionatozinc. As a result, the acrylic group was polymerized, and the reaction solution was slurried. became.
＜比較例１０＞
　実施例４においてビスペンタジオナト亜鉛の代わりにペンタジオナトリチウム（Ｌｉ（ａｃａｃ））を用いた以外は同様にして反応を行ったところ、アクリル基が重合し、反応液はスラリー状になった。 <Comparative Example 10>
In Example 4, the reaction was carried out in the same manner except that pentadionium lithium (Li (acac)) was used instead of bispentadionatozinc. As a result, the acrylic group was polymerized and the reaction solution became a slurry. .
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　前記の実施例および比較例より得られた感光性樹脂を用い、表２に示す配合比率に従って、３本ロールミルにて混練し硬化性樹脂組成物を調製した。次いで上記感光性樹脂組成物を予め脱脂を行なったプリント回路基板に、乾燥膜厚で３０～４０μｍになるようにスクリーン印刷法により塗布し、８０℃で２０分間予備乾燥後、室温まで冷却し乾燥塗膜を得た。この塗膜にレジストパターンを有するネガフィルムを密着させ、紫外線露光装置を用いて、３５０ｍＪ／ｃｍ3露光し、ネガフィルムをはずした後、１％炭酸ナトリウム水溶液を用い、スプレー圧２．０ｋｇｆ／ｃｍ2で６０秒間現像し、未露光部分を溶解除去した。その後、熱風乾燥機を用い、１５０℃で３０分間加熱硬化を行い、試験片を得た。得られた塗膜は、以下に示す試験方法に従って、各種物性評価を行った。この試験の評価結果を表２に示す。 A curable resin composition was prepared by kneading with a three-roll mill according to the blending ratio shown in Table 2 using the photosensitive resins obtained from the above Examples and Comparative Examples. Next, the photosensitive resin composition is applied to a printed circuit board that has been degreased in advance by a screen printing method so that the dry film thickness is 30 to 40 μm, preliminarily dried at 80 ° C. for 20 minutes, then cooled to room temperature and dried. A coating film was obtained. A negative film having a resist pattern is adhered to the coating film, exposed to 350 mJ / cm 3 using an ultraviolet exposure device, and after removing the negative film, a spray pressure of 2.0 kgf / cm using a 1% sodium carbonate aqueous solution is used. Development was performed at 2 for 60 seconds to dissolve away unexposed portions. Thereafter, using a hot air dryer, heat curing was performed at 150 ° C. for 30 minutes to obtain a test piece. The obtained coating film was subjected to various physical property evaluations according to the following test methods. The evaluation results of this test are shown in Table 2.
〔はんだ耐熱性〕
　ＪＩＳ　Ｃ　６４８１の試験方法に従って、２６０℃のはんだ浴への試験片の１０秒浸漬を３回行ない、外観の変化を以下の基準で評価した。結果を表２に示す。また、ポストフラックス（ロジン系）としては、ＪＩＳ　Ｃ　６４８１に従ったフラックスを使用した。
○：外観変化なし。
△：硬化膜の変色が認められるもの。
×：硬化膜の浮き、剥れ、はんだ潜りあり。 [Solder heat resistance]
According to the test method of JIS C 6481, the test piece was immersed in a 260 ° C. solder bath for 10 seconds three times, and the change in appearance was evaluated according to the following criteria. The results are shown in Table 2. Moreover, as a post flux (rosin type), a flux according to JIS C 6481 was used.
○: No change in appearance.
Δ: Discoloration of the cured film is observed.
X: There exists a float of a cured film, peeling, and a solder dive.
〔ＰＣＴ耐性〕
　硬化膜のＰＣＴ耐性を条件１２１℃、飽和蒸気圧下で５０時間にて処理し、以下の基準で評価した。結果を表２に示す。
○：硬化膜にふくれ、剥がれ、変色がないもの。
△：硬化膜に若干ふくれ、剥がれ、変色があるもの。
×：硬化膜にふくれ、剥がれ、変色があるもの。 [PCT resistance]
The cured film was treated for PCT resistance under conditions of 121 ° C. and saturated vapor pressure for 50 hours, and evaluated according to the following criteria. The results are shown in Table 2.
○: The cured film does not blister, peel off or discolor.
Δ: The cured film has some swelling, peeling, and discoloration.
X: The cured film has blistering, peeling and discoloration.
〔接着性〕
　硬化膜をＰＣＴ試験器にて条件１２１℃、飽和蒸気圧下で２４時間処理後、ＪＩＳＤ０２０２の試験方法に従って硬化膜に碁盤目状にクロスカットを入れ、次いでセロハン粘着テープによるピーリングテスト後の剥れの状態を目視判定した。結果を表２に示す。
○：１００／１００で全く剥れのないもの
△：５０／１００～９０／１００
×：０／１００～５０／１００ 〔Adhesiveness〕
After the cured film was treated with a PCT tester under the conditions of 121 ° C. and saturated vapor pressure for 24 hours, according to the test method of JISD0202, a cross cut was put in a grid pattern and then peeled off after a peeling test using a cellophane adhesive tape. The state was judged visually. The results are shown in Table 2.
○: 100/100 with no peeling Δ: 50/100 to 90/100
×: 0/100 to 50/100
〔電気絶縁性〕
　硬化皮膜の電気絶縁性を以下の基準にて評価した。加湿条件：温度１２０℃、湿度８５％ＲＨ、印加電圧３０Ｖ、５０時間。
　測定条件：測定時間６０秒、印加電圧５００Ｖ。
　○：加湿後の絶縁抵抗値１０9Ω以上、銅のマイグレーションなし
　×：加湿後の絶縁抵抗値１０9Ω以下、銅のマイグレーションあり [Electrical insulation]
The electrical insulation of the cured film was evaluated according to the following criteria. Humidification conditions: temperature 120 ° C., humidity 85% RH, applied voltage 30 V, 50 hours.
Measurement conditions: measurement time 60 seconds, applied voltage 500V.
○: Insulation resistance value after humidification of 10 9 Ω or more, no copper migration ×: Insulation resistance value after humidification of 10 9 Ω or less, copper migration
　表２から明らかなように組成例１～４は、ガラス製の反応装置を使用しなくても一般的に使用されているＳＵＳ製の反応装置で製造した感光性樹脂を用いても、ソルダーレジストとしての信頼性を低下させないことを確認した。 As is apparent from Table 2, the composition examples 1 to 4 are solder resists even if a photosensitive resin produced by a commonly used SUS reaction apparatus is used without using a glass reaction apparatus. As a result, it was confirmed that the reliability was not lowered.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002

Claims (4)

  1. 　１分子中に２個以上のフェノール性水酸基を有する樹脂（ａ）のフェノール性水酸基の一部または全部を末端にアルコール性水酸基を有する（ポリ）オキシアルキレン基で鎖延長した樹脂（ｂ）に、重合性不飽和基含有カルボン酸エステル（ｃ）を、亜鉛またはジルコニウムのアセチルアセトン錯体（ｄ）の存在下で、重合性不飽和基が樹脂（ｂ）のアルコール性水酸基１当量に対して０．２～０．８当量となる範囲で導入し、さらに残りのアルコール性水酸基に多塩基酸無水物（ｅ）を反応させることを特徴とする感光性樹脂の製造方法。 Resin (b) in which part or all of the phenolic hydroxyl groups of resin (a) having two or more phenolic hydroxyl groups in one molecule are chain-extended with a (poly) oxyalkylene group having an alcoholic hydroxyl group at the end; The polymerizable unsaturated group-containing carboxylic acid ester (c) is added in an amount of 0.2 to 1 equivalent of the alcoholic hydroxyl group of the resin (b) in the presence of an acetylacetone complex (d) of zinc or zirconium. A method for producing a photosensitive resin, which is introduced in a range of up to 0.8 equivalent, and further, the remaining alcoholic hydroxyl group is reacted with a polybasic acid anhydride (e).
  2. 　前記重合性不飽和基含有カルボン酸エステル（ｃ）が（メタ）アクリル酸エステルである、請求項１に記載の感光性樹脂の製造方法。 The method for producing a photosensitive resin according to claim 1, wherein the polymerizable unsaturated group-containing carboxylic acid ester (c) is a (meth) acrylic acid ester.
  3. 　前記樹脂（ｂ）に残存するフェノール性水酸基の量が樹脂（ａ）のフェノール性水酸基１当量に対して０．２当量以下であることを特徴とする、請求項１または２に記載の感光性樹脂の製造方法。 3. The photosensitive property according to claim 1, wherein the amount of the phenolic hydroxyl group remaining in the resin (b) is 0.2 equivalent or less with respect to 1 equivalent of the phenolic hydroxyl group of the resin (a). Manufacturing method of resin.
  4. 　請求項１～３のいずれか一項に記載の製造方法により得られた感光性樹脂、エポキシ樹脂、光重合開始剤、並びに重合性不飽和化合物および／または溶剤を含む、感光性樹脂組成物。 A photosensitive resin composition comprising a photosensitive resin, an epoxy resin, a photopolymerization initiator, a polymerizable unsaturated compound and / or a solvent obtained by the production method according to any one of claims 1 to 3.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5847918B1 (en) * 2014-12-26 2016-01-27 太陽インキ製造株式会社 Curable resin composition, dry film, cured product and printed wiring board
KR20160079681A (en) * 2014-12-26 2016-07-06 다이요 잉키 세이조 가부시키가이샤 Curable resin composition, dry film, cured product, and printed wiring board
WO2017010534A1 (en) * 2015-07-14 2017-01-19 ローム アンド ハース エレクトロニック マテリアルズ エルエルシー Photosensitive resin composition
JP2017032903A (en) * 2015-08-05 2017-02-09 太陽インキ製造株式会社 Curable resin composition, dry film, cured product, and printed wiring board

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH026517A (en) * 1988-06-24 1990-01-10 Toagosei Chem Ind Co Ltd Preparation of polyester (meth)acrylate
JPH02175746A (en) * 1988-12-28 1990-07-09 Toagosei Chem Ind Co Ltd Curable resin composition
JPH1143524A (en) * 1997-07-29 1999-02-16 Shinnakamura Kagaku Kogyo Kk Calixarene derivative and setting resin composition containing the same
JP2000178330A (en) * 1998-10-05 2000-06-27 Nippon Shokubai Co Ltd Modified novolak resin and its resin composition
JP2003280190A (en) * 2002-03-22 2003-10-02 Taiyo Ink Mfg Ltd Photosetting and thermosetting resin composition
JP2003280189A (en) * 2002-03-22 2003-10-02 Taiyo Ink Mfg Ltd Photosetting and thermosetting resin composition
JP2003280191A (en) * 2002-03-22 2003-10-02 Taiyo Ink Mfg Ltd Photosetting and thermosetting resin composition
JP2004359729A (en) * 2003-06-02 2004-12-24 Taiyo Ink Mfg Ltd Curable composition containing carboxyl-group-containing photosensitive resin
JP2004359728A (en) * 2003-06-02 2004-12-24 Dainippon Ink & Chem Inc Preparation method for carboxy-group-containing photosensitive resin

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58173051A (en) * 1982-03-31 1983-10-11 Sumitomo Deyurezu Kk Resin coated sand for shell mold
JP2006118012A (en) * 2004-10-22 2006-05-11 Nippon Parkerizing Co Ltd Surface treatment agent for metal, surface treatment method for metallic material, and surface-treated metallic material
EP1939231A4 (en) * 2005-09-02 2009-08-26 Mitsui Chemicals Polyurethanes (meth)acylate-grafted polyether polyol, and process for production and use thereof
JP5611698B2 (en) * 2010-07-28 2014-10-22 Ｄｉｃグラフィックス株式会社 Resin composition
JP5586362B2 (en) * 2010-07-28 2014-09-10 Ｄｉｃグラフィックス株式会社 Resin composition
JP5611697B2 (en) * 2010-07-28 2014-10-22 Ｄｉｃグラフィックス株式会社 Resin composition

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH026517A (en) * 1988-06-24 1990-01-10 Toagosei Chem Ind Co Ltd Preparation of polyester (meth)acrylate
JPH02175746A (en) * 1988-12-28 1990-07-09 Toagosei Chem Ind Co Ltd Curable resin composition
JPH1143524A (en) * 1997-07-29 1999-02-16 Shinnakamura Kagaku Kogyo Kk Calixarene derivative and setting resin composition containing the same
JP2000178330A (en) * 1998-10-05 2000-06-27 Nippon Shokubai Co Ltd Modified novolak resin and its resin composition
JP2003280190A (en) * 2002-03-22 2003-10-02 Taiyo Ink Mfg Ltd Photosetting and thermosetting resin composition
JP2003280189A (en) * 2002-03-22 2003-10-02 Taiyo Ink Mfg Ltd Photosetting and thermosetting resin composition
JP2003280191A (en) * 2002-03-22 2003-10-02 Taiyo Ink Mfg Ltd Photosetting and thermosetting resin composition
JP2004359729A (en) * 2003-06-02 2004-12-24 Taiyo Ink Mfg Ltd Curable composition containing carboxyl-group-containing photosensitive resin
JP2004359728A (en) * 2003-06-02 2004-12-24 Dainippon Ink & Chem Inc Preparation method for carboxy-group-containing photosensitive resin

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5847918B1 (en) * 2014-12-26 2016-01-27 太陽インキ製造株式会社 Curable resin composition, dry film, cured product and printed wiring board
KR20160079681A (en) * 2014-12-26 2016-07-06 다이요 잉키 세이조 가부시키가이샤 Curable resin composition, dry film, cured product, and printed wiring board
CN105739241A (en) * 2014-12-26 2016-07-06 太阳油墨制造株式会社 Curable resin composition, dry film, cured product and printed circuit board
KR102457069B1 (en) * 2014-12-26 2022-10-21 다이요 잉키 세이조 가부시키가이샤 Curable resin composition, dry film, cured product, and printed wiring board
WO2017010534A1 (en) * 2015-07-14 2017-01-19 ローム アンド ハース エレクトロニック マテリアルズ エルエルシー Photosensitive resin composition
JP2017021298A (en) * 2015-07-14 2017-01-26 ローム・アンド・ハース電子材料株式会社 Photosensitive resin composition
JP2017032903A (en) * 2015-08-05 2017-02-09 太陽インキ製造株式会社 Curable resin composition, dry film, cured product, and printed wiring board

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