Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
• • 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
• • 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

Definitions

• Patent document 1 CN114716868A
• Patent document 2 CN108137791A
• Patent document 3 CN101798432A
• Patent document 4 CN106380929A
• the object of the present invention is to provide a method for forming a film having excellent adhesion and thermal shock resistance.
• the present inventors have conducted intensive research to solve the above problems and found that the type of filler has a great influence on the thermal shock resistance.
• the following alkaline developing resin composition can solve the above problems, thereby completing the present invention.
• the alkaline developing resin composition is characterized by containing (A) a vinyl ester resin, (B) a photopolymerization initiator, (C) a glass powder, (D) a compound having two or more ethylenically unsaturated groups in one molecule, and (E) an inorganic filler, wherein the (E) inorganic filler comprises talc, and the (C) glass powder comprises SiO2 : 60-65%, Fe2O3 : 0.01-0.02%, Al2O3 : 14-20%, CaO: 6-9% , MgO: 1-2%, and B2O3 : 8-12%, and the Mohs hardness of the (C) glass powder is less than 6.5.
• the photocurable dry film of the present invention is characterized by being obtained by applying the alkaline developing resin composition on a carrier film and drying it.
• the cured product of the present invention is characterized in that it is obtained by photocuring the following coating film, wherein the coating film is: a coating film obtained by applying the alkaline developing resin composition on copper and drying; or a coating film obtained by applying the alkaline developing resin composition on a carrier film and drying it, and laminating the obtained photocurable dry film on copper.
• the printed circuit board of the present invention is characterized in that it is obtained by photocuring and then thermally curing the following coating film, wherein the coating film is: a coating film obtained by coating the alkaline developing resin composition on a substrate having a copper circuit and drying; or a coating film obtained by coating the alkaline developing resin composition on a carrier film and drying, and laminating the obtained photocurable dry film on a substrate having a copper circuit.
• the coating film is: a coating film obtained by coating the alkaline developing resin composition on a substrate having a copper circuit and drying; or a coating film obtained by coating the alkaline developing resin composition on a carrier film and drying, and laminating the obtained photocurable dry film on a substrate having a copper circuit.
• the most significant technical feature of the alkaline developing resin composition of the present invention is that it comprises (A) a vinyl ester resin, (B) a photopolymerization initiator, (C) a glass powder, (D) a compound having two or more ethylenically unsaturated groups in one molecule, and (E) an inorganic filler, wherein the (E) inorganic filler comprises talc, and the (C) glass powder comprises SiO 2 : 60 to 65%, Fe 2 O 3 : 0.01 to 0.1% by weight. 0.02%, Al 2 O 3 : 14-20%, CaO: 6-9%, MgO: 1-2%, B 2 O 3 : 8-12%, and the Mohs hardness of the (C) glass powder is lower than 6.5.
• the adhesion can be improved while maintaining excellent thermal shock resistance.
• talc as a filler has good flexibility and excellent crack resistance in the Temperature Cycle Test (hereinafter sometimes referred to as the "TCT test"), but the adhesion becomes worse as the amount used increases.
• glass powder especially soft composite glass powder, can provide excellent adhesion as a filler, it lacks resistance to thermal shock.
• the present invention can provide an alkali-developable resin composition capable of forming a solder resist having excellent adhesion and thermal shock resistance, a photocurable dry film thereof, a cured product thereof, and a printed wiring board.
• FIG. 1 is a photograph showing cracks in a solder resist film used for evaluating thermal shock resistance in Examples.
• FIG. 2 is a photograph showing that the solder resist film used for evaluating thermal shock resistance in Examples is not cracked.
• the parent rock can be any one of magnesium carbonate, serpentine, silica/silicon dioxide-alumina, and magnesium sediment, and can be one of the so-called silicate minerals, and the shape can be block or fine powder. It can be surface treated or not.
• the average particle size of talc is preferably 1.0-20.0 ⁇ m, more preferably 2.0 to 10 ⁇ m, and further preferably 3.0 to 8.0 ⁇ m.
• HD25 manufactured by Shandong Pingdu Talc Mining Co., Ltd. and LMP-100 manufactured by Fuji Talc Industry Co., Ltd. can be listed.
• silicon dioxide Commercially available products of the silicon dioxide include CS1002 and CS1002A manufactured by Jiangsu Lianrui New Materials Co., Ltd., A-8 manufactured by Sibelco Co., Ltd., SE-40 manufactured by Tokuyama Co., Ltd., MSV25G manufactured by Longsen, MLV-2114 manufactured by Longsen, SO-E5 manufactured by ADMATECHS, and SO-E2 manufactured by ADMATECHS.
• Vinyl ester resins obtained by copolymerizing unsaturated carboxylic acids such as (meth)acrylic acid with one or more other compounds having unsaturated double bonds;
• Photosensitive vinyl ester resins obtained by adding an ethylenically unsaturated group as a pendant group to a copolymer of an unsaturated carboxylic acid such as (meth)acrylic acid and one or more other compounds having an unsaturated double bond, using a compound having an epoxy group and an unsaturated double bond such as glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, or (meth)acryloyl chloride;
• Vinyl ester resins obtained by reacting a polyfunctional epoxy compound with an unsaturated monocarboxylic acid and reacting a saturated or unsaturated polyacid anhydride with the resulting hydroxyl group;
• a vinyl ester resin containing hydroxyl groups and carboxyl groups obtained by reacting a hydroxyl-containing polymer such as a polyvinyl alcohol derivative with a saturated or unsaturated polybasic acid anhydride, and then reacting a compound having an epoxy group and an unsaturated double bond in one molecule with the resulting carboxylic acid;
• a known substance can be used, and examples thereof include: benzoin and alkyl ethers thereof such as benzoin, benzoin methyl ether, and benzoin ethyl ether; acetophenones such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, and 4-(1-tert-butyldioxy-1-methylethyl)acetophenone; anthraquinones such as 2-methylanthraquinone, 2-amylanthraquinone, 2-tert-butylanthraquinone, and 1-chloroanthraquinone; thioxanthones such as isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone, and 2-chlorothioxanthone; ketals such as ace
• alkylphenone-based photopolymerization initiators include ⁇ -hydroxyalkylphenone-based products such as Omnirad 184, Omnirad 1173, Omnirad 2959, and Omnirad 127 manufactured by IGM Resins B.V.
• ⁇ -aminoacetophenone-based photopolymerization initiators include 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholino)phenyl]-1-butanone, and N,N-dimethylaminoacetophenone.
• Commercially available products include Omnirad 907, Omnirad 369, and Omnirad 379 manufactured by IGM Resins B.V.
• acylphosphine oxide-based photopolymerization initiator specifically, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide, trifunctional or higher acylphosphine-based photopolymerization initiators, etc.
• the trifunctional or higher acylphosphine-based photopolymerization initiator may be a photopolymerization initiator having three or more acylphosphine oxide skeletons in one molecule, and may be represented by the following formula (I).
• n is an integer between 3 and 8;
• R1 and R2 are independently C1 - C18 alkyl, C6 - C12 aryl and C5 -C12 cycloalkyl, each of which is not disconnected or is disconnected by the following groups: one or more oxygen and/or sulfur atoms and/or one or more substituted or unsubstituted imino groups, or R1 and R2 are independently a five- to six -membered heterocyclic group containing oxygen and/or nitrogen and/or sulfur atoms, wherein the aforementioned groups are each optionally substituted by aryl, alkyl, aryloxy, alkoxy, Heteroatom and/or heterocyclic group substitution;
• Y is O or S
• R 3 is hydrogen or C 1 to C 4 alkyl
• the photopolymerization initiator of formula (I) does not contain a photocurable ethylenically unsaturated group.
• the content of the epoxy resin (G) is preferably 10 to 100 parts by weight, more preferably 20 to 90 parts by weight, and even more preferably 30 to 80 parts by weight, based on 100 parts by weight of the vinyl ester resin (A) in terms of solid content.
• organic solvents examples include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, and petroleum-based solvents. More specifically, they include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; glycol ethers such as cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, and triethylene glycol monoethyl ether; esters such as ethyl acetate, butyl acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethy
• the alkaline developing type resin composition can also be used in the form of a photocurable dry film obtained by applying the alkaline developing type resin composition on a carrier film in advance and drying.
• a photocurable dry film obtained by applying the alkaline developing type resin composition on a carrier film in advance and drying. The following shows the case where the alkaline developing type resin composition of the present invention is used in the form of a photocurable dry film.
• the photocurable dry film has a structure in which a carrier film, a resin layer, and a peelable cover film used as needed are sequentially laminated.
• the resin layer is a layer obtained by coating the alkaline developing resin composition of the present invention on a carrier film and drying it. After the resin layer is formed on the carrier film, the cover film is laminated thereon to obtain a photocurable dry film.
• the alkaline developing resin composition is suitably used for forming a cured film on a printed circuit board.
• the cured film is preferably a permanent insulating film, and particularly preferably a solder resist layer.
• the carboxyl vinyl ester resin of Synthesis Example A has a solid content of 65%, which is equivalent to the carboxyl vinyl ester resin of (5).
• Pigment F Phthalocyanine Green, Pigment A manufactured by Dainippon Ink & Chemicals Co., Ltd.
• F defoamer KS-66, manufactured by Shin-Etsu Chemical Co., Ltd.
• F dispersant BYK-110, polyphosphate ester, manufactured by BYK Chemical
• C soft composite glass powder K10, manufactured by Suzhou Jinyi New Material Technology Co., Ltd. (SiO 2 : 62.3-62.8%, Fe 2 O 3 : 0.0149-0.017%, Al 2 O 3 : 16.9-17.6%, CaO: 7.35-7.66%, MgO: 1.4-1.54%, B 2 O 3 : 9.6-10.3%), Mohs hardness: 5-6
• Epoxy resin N-770-75EA, manufactured by DIC Corporation, novolac type multifunctional epoxy resin, solid content 75%
• the alkaline developing resin composition of the embodiment and the comparative example was applied to the entire surface of the substrate having a 2 mm copper wire pattern formed thereon by screen printing in a manner to a thickness of 40 ⁇ m, and dried at 80° C. for 30 minutes in a hot air circulation drying oven. After cooling to room temperature, the pattern was exposed at 300 mJ/cm 2 using an exposure device equipped with a high-pressure mercury lamp, and then developed for 60 seconds in a 1 wt % sodium carbonate aqueous solution, a pressure of 0.2 MPa, and a liquid temperature of 30° C., and then cured at 150° C. for 60 minutes in a hot air circulation drying oven. Thus, a copper circuit substrate having a cured film was prepared.
• a PosiTest AT digital display pull-off adhesion tester (which can measure the adhesion of metal, concrete and other material coatings) from DeFelsko, USA, was prepared.
• An ingot (size: 1 cm in bottom diameter) (as shown in the schematic diagram of FIG. 3 ) was adhered and fixed (heated at 120° C. for 1 hour) to the surface of the above-mentioned cured film using the American Emerson Cumming adhesive (LOCTITE ABLESTIK 2332-17 high-strength structural adhesive) to measure the tensile force required to separate the cured film per unit area from the copper substrate, expressed in MPa, and measured in accordance with ATSM D4541.
• the American Emerson Cumming adhesive LOCTITE ABLESTIK 2332-17 high-strength structural adhesive
• the alkaline developing resin composition of the embodiment and the comparative example is applied to the entire surface of a substrate having a 2 mm copper wire pattern formed thereon by screen printing in a manner to a thickness of 40 ⁇ m, and dried in a hot air circulation drying furnace at 80°C for 30 minutes. After cooling to room temperature, the pattern is exposed at 400 mJ/cm2 using an exposure device equipped with a high-pressure mercury lamp, followed by development for 60 seconds in a 1 wt % sodium carbonate aqueous solution, a pressure of 0.2 MPa, and a liquid temperature of 30°C, and then cured in a hot air circulation drying furnace at 150°C for 60 minutes.
• a hot and cold cycle crack resistance evaluation substrate having 17 resist patterns having a right angle shape is produced by irradiating with ultraviolet rays in a UV conveyor furnace at a cumulative exposure of 2000 mJ/cm2.
• a plurality of the above-mentioned The prepared evaluation substrate was placed in a hot and cold cycle machine that cycles the temperature between -40°C and 160°C and set different cycle times to conduct a hot and cold shock cycle test (TCT test). Then, the appearance at each cycle number was observed, and the maximum cycle number without cracks was recorded (for the presence or absence of cracks, see Figures 1 and 2).
• TCT test hot and cold shock cycle test

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• Physics & Mathematics (AREA)
• General Physics & Mathematics (AREA)
• Engineering & Computer Science (AREA)
• Manufacturing & Machinery (AREA)
• Microelectronics & Electronic Packaging (AREA)
• Spectroscopy & Molecular Physics (AREA)
• Non-Metallic Protective Coatings For Printed Circuits (AREA)
• Materials For Photolithography (AREA)
• Laminated Bodies (AREA)
• Macromonomer-Based Addition Polymer (AREA)
• Epoxy Resins (AREA)
• Polymerisation Methods In General (AREA)
• Paints Or Removers (AREA)

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