WO2012029806A1 - Method for producing photosensitive resin and photosensitive resin composition - Google Patents
Method for producing photosensitive resin and photosensitive resin composition Download PDFInfo
- 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
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- resin
- group
- hydroxyl group
- photosensitive resin
- polymerizable unsaturated
- Prior art date
Links
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.
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- General Chemical & Material Sciences (AREA)
- Materials For Photolithography (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
Description
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.
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.
〔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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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. .
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.
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.
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
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
Claims (4)
- 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).
- 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.
- 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.
- 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.
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020137004223A KR101468341B1 (en) | 2010-09-03 | 2011-08-30 | Method for producing photosensitive resin and photosensitive resin composition |
CN201180042400.3A CN103080168B (en) | 2010-09-03 | 2011-08-30 | Method for producing photosensitive resin and photosensitive resin composition |
JP2012531902A JP5875519B2 (en) | 2010-09-03 | 2011-08-30 | Photosensitive resin and method for producing photosensitive resin composition containing the photosensitive resin |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2010-197628 | 2010-09-03 | ||
JP2010197628 | 2010-09-03 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2012029806A1 true WO2012029806A1 (en) | 2012-03-08 |
Family
ID=45772887
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2011/069647 WO2012029806A1 (en) | 2010-09-03 | 2011-08-30 | Method for producing photosensitive resin and photosensitive resin composition |
Country Status (5)
Country | Link |
---|---|
JP (1) | JP5875519B2 (en) |
KR (1) | KR101468341B1 (en) |
CN (1) | CN103080168B (en) |
TW (1) | TWI525133B (en) |
WO (1) | WO2012029806A1 (en) |
Cited By (4)
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)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR102319968B1 (en) * | 2018-09-28 | 2021-10-29 | 삼성에스디아이 주식회사 | Positive photosensitive resin composition, photosensitive resin layer and electronic device using the same |
Citations (9)
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)
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 |
-
2011
- 2011-08-30 WO PCT/JP2011/069647 patent/WO2012029806A1/en active Application Filing
- 2011-08-30 CN CN201180042400.3A patent/CN103080168B/en active Active
- 2011-08-30 KR KR1020137004223A patent/KR101468341B1/en active IP Right Grant
- 2011-08-30 JP JP2012531902A patent/JP5875519B2/en active Active
- 2011-09-02 TW TW100131700A patent/TWI525133B/en active
Patent Citations (9)
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)
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 |
Also Published As
Publication number | Publication date |
---|---|
KR20130041229A (en) | 2013-04-24 |
CN103080168B (en) | 2014-10-01 |
TW201229095A (en) | 2012-07-16 |
TWI525133B (en) | 2016-03-11 |
CN103080168A (en) | 2013-05-01 |
JPWO2012029806A1 (en) | 2013-10-31 |
JP5875519B2 (en) | 2016-03-02 |
KR101468341B1 (en) | 2014-12-03 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JPWO2002024774A1 (en) | Carboxyl group-containing photosensitive resin, alkali-developable photo-curable / thermo-curable composition containing the same, and cured product thereof | |
JP3134037B2 (en) | Thermosetting or photocuring / thermosetting coating composition using melamine organic acid salt | |
WO2002077058A1 (en) | Resin curable with actinic energy ray, photocurable/thermosetting resin composition containing the same, and cured article obtained therefrom | |
JP5875519B2 (en) | Photosensitive resin and method for producing photosensitive resin composition containing the photosensitive resin | |
JP6111248B2 (en) | Alkali developable resin and photosensitive resin composition using the same | |
JP2008020632A (en) | Photocurable/heat curable one-liquid type solder resist composition and printed wiring board using same | |
KR101267111B1 (en) | Photosensitive resin composition and method for producing photosensitive resin used therein | |
JPH07103213B2 (en) | Resin composition containing unsaturated group-containing polycarboxylic acid resin and solder resist resin composition | |
JP3953854B2 (en) | Photo-curing / thermosetting resin composition | |
JP4011885B2 (en) | Method for producing curable resin and composition containing curable resin | |
JP2007197530A (en) | Curable composition and cured product thereof | |
JP4400926B2 (en) | Photosensitive resin composition and cured product thereof | |
JP2003280190A (en) | Photosetting and thermosetting resin composition | |
JP4682340B2 (en) | Method for producing photosensitive resin | |
JP2003167331A (en) | Resin composition and cured body thereof | |
JP5356211B2 (en) | Photosensitive resin manufacturing method, photosensitive resin and photosensitive resin composition obtained from the manufacturing method | |
JP2963069B2 (en) | Solder photoresist ink composition | |
JP4889850B2 (en) | Curable resin, photosensitive resin composition, and method for forming cured coating film | |
JP4426123B2 (en) | Curable resin and curable resin composition | |
US20170363958A1 (en) | Low dk/df solder resistant composition use for printed circuit board | |
JP4989435B2 (en) | Photosensitive resin and photosensitive resin composition | |
JP2001264977A (en) | Photosensitive resin composition | |
JP2003280191A (en) | Photosetting and thermosetting resin composition | |
JP5133104B2 (en) | Epoxy (meth) acrylate resin, photocurable / thermosetting resin composition containing the same, and cured product thereof | |
JP6755007B2 (en) | Unsaturated group-containing alkali-soluble resin |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 201180042400.3 Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 11821821 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2012531902 Country of ref document: JP |
|
ENP | Entry into the national phase |
Ref document number: 20137004223 Country of ref document: KR Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 11821821 Country of ref document: EP Kind code of ref document: A1 |