Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
  • C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
• • 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
  • G03F7/0048—Photosensitive materials characterised by the solvents or agents facilitating spreading, e.g. tensio-active agents
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
  • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
• • 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
  • G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
• • 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
  • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
  • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K3/00—Apparatus or processes for manufacturing printed circuits
  • H05K3/22—Secondary treatment of printed circuits
  • H05K3/28—Applying non-metallic protective coatings
  • H05K3/285—Permanent coating compositions
  • H05K3/287—Photosensitive compositions

Definitions

• the present invention relates to a liquid photo solder resist composition and a photo solder resist film thereof. More particularly, the present invention relates to a photo solder resist film that includes an epoxy resin of an isocyanurate structure containing one epoxy group and at least two acryl groups in addition to the conventional liquid photo solder resist composition to have UV-curing and thermosetting properties and provide a high-density ultrafine conductive pattern developable with an aqueous alkali solution, thereby being useful as a protection film for printed circuit boards and color filters.
• the solder resist is a coating material used to protect selected areas of a printed circuit board from the action of solder, so it is required to have excellent properties in a very wide range, including adhesion, dielectric resistance, resistance to solder temperature, resistance to solvent, resistance to alkaline and acid, resistance to plating, etc.
• the liquid photo solder resist developable with an aqueous alkali solution has some advantages over the conventional UV-curing. and thermosetting solder mask using a pattern forming screen in that it allows the formation of a high-density ultrafine pattern.
• the conventional liquid photo solder resist of which the composition includes a heat-activated epoxy compound is, however, problematic in that the carboxyl group bonded to the side chain of a UV-curing resin developable with an aqueous alkali solution, or a thermosetting catalyst is heat-activated with the epoxy groups during a drying step, as a result of which the areas not exposed to the ultraviolet (UV) light cannot be completely developed with the aqueous alkali solution to leave residues.
• the epoxy resins are mostly so poor in light transmittance as to cause a problem in forming a fine circuit of the solder resist, so the content of the epoxy compound in the composition must be limited within a narrow range.
• solder resist that solves these problems.
• a photo solder resist prepared from a liquid photo solder resist composition comprising an epoxy resin of an isocyanurate structure containing one epoxy group and at least two UV-curing or thermosetting acryl groups in one molecule in addition to the conventional liquid photo solder resist composition guarantees a wide dry control width without surface stickiness and provides excellent properties such as resistance to solder heat, resolution, resistance to plating, and resistance to acid/alkali solutions, thereby being useful for a protection film of printed circuit boards and color filters having a high-density ultrafine conductive pattern.
• the liquid photo solder resist composition of the present invention which includes a UV-curing resin developable with an aqueous alkali solution, a UV-reactive acrylic monomer, an epoxy resin, a photo-polymerization initiator, and an organic solvent, is characterized in that the epoxy resin is of an isocyanurate structure comprising one epoxy group and at least two acryl groups in one molecule as prepared by steps comprising: (a) reacting a cyanurate compound with an acrylate-based monomer to yield a product having acryl groups; and (b) adding an epichlorohydrin to the product of the step for introducing epoxy group(a).
• the present invention includes a photo solder resist film prepared from the liquid photo solder resist composition.
• the present invention is directed to a liquid photo solder resist composition of the present invention, which includes a UV-curing resin developable with an aqueous alkali solution, a UV-reactive acrylic monomer, an epoxy resin, a photo-polymerization initiator, and an organic solvent, the epoxy resin being of an isocyanurate structure comprising one epoxy group and at least two acryl groups in one molecule as prepared by steps comprising: (a) reacting a cyanurate compound with an acrylate-based monomer to yield a product having acryl groups; and (b) adding an epichlorohydrin to the product of the step (a).
• Epoxy resin as used herein is of an isocyanurate structure comprising one epoxy group and at least two acryl groups in one molecule as prepared by steps comprising: (a) reacting a cyanurate compound with an acrylate-based monomer to yield a product having acryl groups; and (b) adding an epichlorohydrin to the product of the step (a).
• the epoxy resin of the present invention has acryl groups introduced by reacting a cyanurate compound with an acrylate-based monomer.
• the cyanurate compound as used herein includes cyanurate(l,3,5-triazine-2,4,6-triol), l,3,5-tris(2-hydroxyethyl) cyanurate, tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, etc.
• the acrylate-based monomer as used herein includes (meth)acrylate, 2-hydroxy ethyl(meth)acrylate, hydroxy propyl(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6- hexanediol di(meth)acrylate, etc.
• the second step is for adding an epichlorohydrine to the resultant product to introduce epoxy groups.
• the epoxy resin thus prepared is of an isocyanurate structure containing one epoxy group and at least two acryl groups in one molecule.
• the specific examples of the epoxy resin include the compounds represented by the following formula 1 or 2.
• R' is methyl, ethyl, or propyl
• R 5 , R 6 , and R 7 are independently a hydrogen, or
• the epoxy resin of the present invention may further include a step of reacting a cyanurate compound with a diol to produce an intermediate prior to the step of introducing acryl groups.
• the cyanurate compound as used herein includes the same compounds as used in the step of introducing acryl groups.
• the diol as used herein includes aliphatic diols such as ethyleneglycol, propyleneglycol, butanediol, pentanediol, or hexanediol; or aromatic diols such as 1-phenyl 1,2-ethanediol, resorcinol, or xylenediol.
• the epoxy resin thus prepared is also of an isocyanurate structure containing one epoxy group and at least two acryl groups in one molecule.
• the specific examples of the epoxy resin include the compounds represented by the following formula 3.
• the epoxy resin of the present invention as used herein can also be of an isocyanurate-structure-containing one epoxy group and ' at least twd acryl group-Tin one " molecule as prepared by a ring opening reaction of an acrylate-based monomer and an epoxy resin of an isocyanurate structure having a plurality of epoxy groups in one molecule.
• the specific examples of the epoxy resin of an isocyanurate structure having a plurality of epoxy groups in one molecule include tris(2,3-epoxypropyl) isocyanurate, l,3,5-tris(2-glycydoxyethyl) cyanurate; or an epoxy compound prepared by ring-opening the epoxy group of tris(2,3-epoxypropyl) isocyanurate or l,3,5-tris(2-glycydoxyethyl) cyanurate with a diol or a dicarbonate compound and then adding an epichlorohydrin to introduce epoxy group.
• the acrylate-based monomer as used herein is the same as previously described.
• the epoxy resin of an isocyanurate structure having a plurality of epoxy groups in one molecule is reacted with the acrylate-based monomer at a mole ratio of 1 :2.
• the epoxy resin thus prepared is also of an isocyanurate structure having one epoxy group and at least two acryl groups in one molecule.
• the specific example of the epoxy resin includes a compound represented by the following formula 4.
• the epoxy resins of an isocyanurate structure having one epoxy group and at least two acryl groups in one molecule as represented by the formulas 1 to 4 can be used alone or in combination with an epoxy resin having at least two epoxy groups in one molecule.
• the epoxy resin of an isocyanurate structure having one epoxy group and at least two acryl groups in one molecule is used in combination with an epoxy resin having at least two epoxy groups in one molecule at a mixing ratio of 30:70 to 99:1.
• the specific examples of the epoxy resin having at least two epoxy groups in one molecule include phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bromobisphenol A type epoxy resin, bisphenol S type epoxy resin, triphenol methane type epoxy resin, rubber-modified epoxy resin such as butadiene nitrile-modified epoxy resin, urethane-modified epoxy resin, polyol-modified epoxy resin, naphthol novolak type epoxy resin, triglycidyl isocyanurate, bixylenol type epoxy resin (e.g., Epikote YX-4000H or YX-612H supplied from JER), diglycidyl phthalate resin, etc.
• phenol novolak type epoxy resin cresol novolak type epoxy resin
• bisphenol A type epoxy resin bisphenol F type epoxy resin
• bromobisphenol A type epoxy resin bisphenol S type epoxy resin
• triphenol methane type epoxy resin rubber-modified epoxy
• the use of the epoxy resin having at least two epoxy groups in one molecule in combination with the epoxy resin of an isocyanurate structure containing one epoxy group and at least two acryl groups in one molecule may enhance a part of the properties such as whether resistance and flexibility which are poor when the epoxy resin having at least two epoxy groups in one molecule is used alone.
• the total content of the epoxy resin used in the present invention is 1 to 50 parts by weight, preferably 5 to 20 parts by weight with respect to 100 parts by dry weight of the UV-curing resin developable with an aqueous alkali solution.
• UV-reactive acrylic monomer The present invention includes at least one UV-reactive acrylic monomer of an isocyanurate structure as represented by the following formulas 5 to 8.
• Rj, R 5 and R 6 are independently a hydrogen, or methyl.
• Formula 7 where R 7 , R 8 , R and Rio are independently a hydrogen, or methyl.
• the UV-reactive acrylic monomer represented by the formulas 5 to 8 is used alone or in combination with the following UV-reactive ethylene- based unsaturated monomer.
• the UV-reactive acrylic monomer is used in combination with the UV-reactive ethylene-based unsaturated monomer at a mixing ratio of 30:70 to 99:1. With the mixing ratio of the UV-reactive acrylic monomer out of the above range, resistance to solder heat and resistance to plating are deteriorated.
• UV-reactive ethylene-based unsaturated monomer examples include 2-hydroxyethyl(meth)acrylate, 2-hydroxypropyl(meth)acrylate, tetrahydrofurfuryl(meth)acrylate, 2-phenoxyethyl(meth)acrylate, glycidyl(meth)acrylate, isobonyl(meth)acrylate, caprolactone (meth)acrylate, ethoxylated (meth)acrylate, propoxylated (meth)acrylate, ethyleneglycol di(meth)acrylate, propyleneglycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, polyethyleneglycol di(meth)acrylate, polypropyleneglycol di(meth)acrylate, ethoxylated bisphenol A di(meth)acrylate, propoxylated bisphenyl A di(
• the total content of the UV-reactive acrylic monomer used in the present invention is 1 to 40 parts by weight, preferably 3 to 15 parts by weight with respect to 100 parts by dry weight of the UV-curing resin developable with an aqueous alkali solution, thereby allowing the formation of a solder resist pattern according to the UV-curing property and providing a resistance to solder heat.
• UV-curing resin developable with aqueous alkali solution The UV-curing resin developable with an aqueous alkali solution in the present invention has at least two ethylene-based unsaturated bonds in one molecule and specifically includes the final products of the following synthesis mechanisms.
• the partial or complete ester reaction between a novolak type epoxy compound and an ethylene-based unsaturated carboxylic acid opens the epoxy group to generate a secondary hydroxy 1 group. Then, a multifunctional acid anhydride is added to the secondary hydroxyl group to yield the final product of the addition reaction.
• the partial or complete ester reaction between a triphenolmethane type epoxy compound and an unsaturated carboxylic acid opens the epoxy group to generate a secondary hydroxyl group. Then, a multifunctional acid anhydride is added to the secondary hydroxyl group to yield the final product of the addition reaction.
• the partial or complete ester reaction between a bisphenol type epoxy compound and an unsaturated carboxylic acid opens the epoxy group to generate a secondary hydroxyl group.
• a multifunctional acid anhydride is added to the secondary hydroxyl group to yield the final product of the addition reaction.
• Glycidyl(meth)acrylate is used for polymerization of an acryl copolymer.
• the partial or complete ester reaction between the acryl copolymer and an unsaturated carboxylic acid opens the epoxy group to generate a secondary hydroxyl group.
• a multifunctional acid anhydride is added to the secondary hydroxyl group to yield the final product of the addition reaction.
• the specific examples of the unsaturated carboxylic acid as used herein include compounds having one ethylene-based unsaturated group, such as methacrylic acid, cinnamic acid, alpha-cyancinnamic acid, crotonic acid, 2-methacryloyl hydroxy ethyl phthalic acid, 2-methacryloyl hydroxy ethyl hexa hydrophthalic acid, etc; or esterification products of multifunctional acrylic compounds having a hydroxyl group, such as trimethylol propane di(meth)acrylate, pentaerithritol tri(meth)acrylate, dipentaerithritol penta(meth)acrylate, etc., compounds having at least two carboxyl groups, or compounds having at least one carboxylic anhydride.
• ethylene-based unsaturated group such as methacrylic acid, cinnamic acid, alpha-cyancinnamic acid, crotonic acid, 2-methacryloyl hydroxy
• the multifunctional acid anhydride as used herein includes succinic anhydride, maleic anhydride, methylsuccinic anhydride, phthalic anhydride, itaconic anhydride, chlorendic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, etc.
• succinic anhydride maleic anhydride
• methylsuccinic anhydride phthalic anhydride
• itaconic anhydride chlorendic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, etc.
• malic anhydride, tetrahydrophthalic anhydride, and hexahydrophthalic anhydride are preferred in the present invention. 4.
• Photopolymerization initiator examples include benzoin alkyl ethers, such as 2-methyl-l-[4-(methylthio)phenyl]-2-(4-morphorinyl)-l-propanone, 2-benzyl-2-(dimethylamino)-l-[4-(4-mo ⁇ phorinyl)phenyl]-l-butanone, bis(etha 5-2,4- cyclopentadiene- 1 -yl)bis[2,6-difluoro-3-( lH-pyrol- 1 -yl)phenyl]titanium, phosphine oxide phenyl bis(2,4,6-trimethylbenzoyl), benzoin, benzoin methyl ether, etc.; anthraquinones, such as 2-ethylanthraquinone, 1-chloroanthraquinone, etc.; thioxantones, such as 2-ethylanthraquinone,
• the photopolymerization initiator can be used
• tertiary amines can be added that include ethyl 4-(dimethylamino) benzoate, 2- ethylhexyl 4-(dimethylamino) benzoate, 2-(dimethylamino)ethyl benzoate, triethanol amine, etc.
• the content of the photopolymerization initiator of the present invention is in the range of 0.1 to 20 wt.% in the photo solder resist composition except for the organic solvent, and preferably 1 to 10 wt.%, which range guarantees active UV-photokinesis. 5.
• Organic solvent examples include aliphatic hydrocarbons, such as hexane, octane, decane, etc.; aromatic hydrocarbons, such as ethylbenzene, propylbenzene, toluene, xylene, etc.; alcohols, such as ethanol, propanol, isopropanol, butanol, 2-methoxypropanol, hexanol, etc.; glycol ethers, such as diethylene glycol monoethylether, diethylene glycol monomethylether, dipropylene glycol monomethylether, etc.; ethers, such as diethylene glycol monoethyl ether acetate, etc; ketones, such as acetone, methylethylketone, etc.; or petroleum solvents, such as solvent naphtha, petroleum naphtha, etc.
• aromatic hydrocarbons such as ethylbenzene, propylbenzene, toluene, xylene
• the organic solvent can be used alone, or as a mixture of at least two of the above solvents in consideration of solubility in the UV-curing resin developable with a diluted aqueous alkali solution, and drying condition.
• the liquid photo solder resist composition of the present invention may include, in addition to the aforementioned components, organic powder, an additive such as an antifoaming agent, a thermosetting enhancer, a pigment, a UV-curing oligomer or polymer, a high molecular weight polymer.
• the specific examples of the inorganic powder include barium sulfate, titanium dioxide, silica, talc, aluminum oxide, calcium carbonate, barium titanate, zinc oxide, bentonite, etc.
• the inorganic powder can be used alone or as a mixture of at least two of the above inorganic powders as sufficiently dispersed in a UV-curing resin developable with a diluted aqueous alkali solution, in consideration of its particle type and size.
• the liquid photo solder resist composition can include a coloring agent such as phthalocyanine green, phthalocyanine blue, diazo yellow, infusibility azo dyestuff, crystal violet, or carbon black; a silicon- or acryl-based antifoaming agent; a leveling agent; or a fluidity enhancer such as a fluidity inhibitor.
• thermosetting rate of the solder resist composition of the present invention there can be used dicyandiamide, dicyandiamide derivatives, melamine, melamine organic acid, melamine derivatives, imidazoles such as 2-methyl imidazole, 2-ethyl-4-methyl imidazole, or 2-phenyl-4-methyl imidazole; imidazole derivatives, urea, urea derivatives, complex of boron trifluoride, phenols, triphenyl phosphine, tertiary amines (e.g., triethyl amine), multifunctional anhydride, or quaternary ammonium salts, which compounds can be used alone or as a mixture of at least two of them in consideration of the dry control width.
• imidazoles such as 2-methyl imidazole, 2-ethyl-4-methyl imidazole, or 2-phenyl-4-methyl imidazole
• imidazole derivatives imidazole derivatives, urea, ure
• the preparation of a photo solder resist from the UV-curing and thermosetting resin composition of the present invention can be described in detail as follows.
• the liquid photo solder resist composition of the present invention is coated on a substrate (generally, an epoxy substrate with a copper film) with a screen, spray, curtain, dip, roll, or spin type printer to form a liquid photo solder resist of an appropriate
• the substrate is then dried at 60 to 100 °C to volatilize the solvent portion.
• the drying is performed at 70 to 85 °C for an appropriate drying time that is
• the substrate is cooled down to the room temperature (15 to 25 °C), and a
• negative mask having a desired pattern is applied onto the substrate directly or indirectly.
• the substrate with the negative mask is then exposed to the UV light.
• the specific examples of the UV lamp as used herein include low pressure mercury lamp, medium pressure mercury lamp, high pressure mercury lamp, ultrahigh pressure mercury lamp, xenon lamp, metal halide lamp, etc. Among these lamps, high pressure mercury lamp, or metal halide lamp is preferred.
• the areas of the solder resist not exposed to the UV light are developed with an aqueous alkali solution to form a solder resist pattern.
• thermosetting component of the photo solder resist 160 °C to cure the thermosetting component of the photo solder resist, thereby providing
• the UV-curing process can be performed once more so as to complete the reaction of the unreacted UV-curing component and improve the properties (e.g., surface tension) of the surface of the photo solder resist.
• the specific examples of the aqueous alkali solution used in the development step include aqueous solutions of sodium carbonate, potassium carbonate, ammonium carbonate, sodium bicarbonate, or potassium bicarbonate. The aqueous solution of sodium carbonate is most preferred.
• a silicon- or acryl-based antifoaming agent can be used to inhibit the formation of bubbles in the development solution.
• the aqueous alkali solution can be substituted by a suspension such as organic amines (e.g., ethanol amine, diethanol amine, triethanol amine, isopropanol amine, diisopropanol amine, etc.).
• organic amines e.g., ethanol amine, diethanol amine, triethanol amine, isopropanol amine, diisopropanol amine, etc.
• TEPIC-SP triglycidyl isocyanurate
• solder resist compositions represented in Table 1 are used to prepare the respective liquid photo solder resist film solutions.
• the film solutions thus prepared were subjected to the following processes to obtain a photo solder resist film of the present invention.
• Coating (Printing) Each photo solder resist coating solution was uniformly coated on a copper
• the copper laminate coated with the photo solder resist was placed in a 80 °C
• Dry control width refers to a drying condition that maintains the developability for complete development without residues in the step of drying the solvent after the printing.
• the photo solder resist was uniformly coated on a copper laminate
• the photo solder resist was then cooled down to 15 to 25 °C.
• the photo solder resist was uniformly coated on a copper laminate substrate in a
• solder resist was then cooled down to 15 to 25 °C. When the surface temperature of the solder resist reached
• ⁇ Easy to peel the mask off, with a trace of the mask on the surface of the solder resist.
• x Difficult to peel the mask off.
• laminate substrate in a thickness of 50 ⁇ m (based on the surface of the copper film) and
• the solder resist was reduced to about 35 ⁇ m due to the volume of the dried solvent.
• solder resist was then cooled down to 15 to 25 °C.
• solder resist reached about 20 °C, a negative mask with circuit widths of 30, 40, 50, 60, 70,
• the substrate was
• Adhesion strength test After the curing step, a cross-cut adhesion strength test was performed on a copper laminate substrate printed with the photo solder resist according to the JIS D 0202 (Japanese Industrial Standards). O : No lattice taken off from the substrate. ⁇ : 1 to 10 lattices taken off from the substrate. x : At least 10 lattices taken off from the substrate.
• the coating thickness was 5 ⁇ m for nickel and 0.08 ⁇ m
• ⁇ The adhesive tape is slightly sustained with the solder resist.
• x The adhesive tape is sustained with lots of the solder resist from the substrate.
• the coating thickness was 0.8 ⁇ m.
• solder resist of the present invention in regard to the resistance to acids, an adhesive tape was adhered to the surface of the solder resist and then detached from the solder resist. At this time, the residue of the solder resist on the adhesive tape was observed and the results were analyzed as follows. O : The adhesive tape is not sustained with the solder resist.
• ⁇ The adhesive tape is slightly sustained with the solder resist.
• x The adhesive tape is sustained with lots of the solder resist from the substrate.
• solder resist of the present invention in regard to the resistance to base, an adhesive tape was adhered to the surface of the solder resist and then detached from the solder resist. At this time, the residue of the solder resist on the adhesive tape was observed and the results were analyzed as follows.
• O The adhesive tape is not sustained with the solder resist.
• ⁇ The adhesive tape is slightly sustained with the solder resist,
• x The adhesive tape is sustained with lots of the solder resist from the substrate. Table 1.
• E Photo-polymerization Enhancer (EHA (9)
• BPF type epoxy-modified binder polymer a UV-curing resin developable with a diluted aqueous alkali solution prepared by reacting an unsaturated mono-carboxylic acid and a multifunctional anhydride with a bisphenol F type epoxy, the content of solvent being 35 % (as supplied by Japan Chemicals Company).
• Novolak type epoxy-modified binder polymer a UV-curing resin developable with a diluted aqueous alkali solution prepared by reacting an unsaturated mono- carboxylic acid and a multifunctional anhydride with a cresol novolak type epoxy, the content of solvent being 35 % (as supplied by Japan Chemicals Company).
• YDCN 500 90P a cresol novolak type epoxy resin having at least two epoxy groups in one molecule (supplied by Kukdo Chemical Co., Ltd. in Korea).
• EPIKOTE 828 a bisphenol A type epoxy resin having two epoxy groups in one molecule (supplied by JER Co., Ltd. in Japan).
• TEPIC-SP a tris(2,3-epoxy propyl)isocyanurate type epoxy resin having three epoxy groups in one molecule (supplied by Nissan Chemical Industries, Ltd.).
• A-DPH a 5- or 6-functional UV-reactive acrylic monomer (supplied by New Nakamura Chemicals. Ltd.).
• IRGACURE-907 a photopolymerization initiator of a 2-methyl-l-[4- (methylthio)phenyl]-2-(4-morphorinyl)-l-propanone structure (supplied by Ciba Geigy).
• DETX a photopolymerization initiator of a 2,4-diethyl thioxantone structure (supplied by Remson Company).
• EHA a photopolymerization enhancer of a 2-ethylhexyl-4-
• Fluid 200 a silicon anti-foaming agent (supplied by Dow Corning Corp.).
• the resist films prepared from the liquid photo solder resist compositions (Examples 1 to 9) of the present invention show a wide dry control width and excellent process characteristics without surface stickiness.
• Their cured film properties such as resistance to solder heat, resolution, resistance to plating, resistance to acids, and resistance to alkali solutions are also very excellent.
• the epoxy resin of an isocyanurate structure containing one epoxy group and at least two acrylic groups in one molecule and the UV-reactive acrylic monomer according to the present invention have an isocyanurate structure excellent in regard to light transmittance and adherence strength to copper films, resulting in an enhanced resistance to plating.
• the epoxy resin of an isocyanurate structure containing one epoxy group and at least two acrylic groups in one molecule and the UV-reactive acrylic monomer according to the present invention have an isocyanurate structure excellent in regard to light transmittance and adherence strength to copper films, so the photo solder resist film prepared from the UV-curing and thermosetting solder resist composition allows the formation of a fine solder resist pattern having a circuit width of less than 50
• electrolytic nickel plating resistance to substitution gold plating, resistance to substitution tin plating, and adherence to the printed circuit board, with enhanced resistance to chemicals.

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