WO2022030324A1 - 導電ペースト、プリント配線板、プリント配線板の製造方法、プリント回路板の製造方法 - Google Patents

導電ペースト、プリント配線板、プリント配線板の製造方法、プリント回路板の製造方法 Download PDF

Info

Publication number
WO2022030324A1
WO2022030324A1 PCT/JP2021/027862 JP2021027862W WO2022030324A1 WO 2022030324 A1 WO2022030324 A1 WO 2022030324A1 JP 2021027862 W JP2021027862 W JP 2021027862W WO 2022030324 A1 WO2022030324 A1 WO 2022030324A1
Authority
WO
WIPO (PCT)
Prior art keywords
conductive paste
film
conductive
elastic modulus
storage elastic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2021/027862
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
水口創
伊月直秀
田島いづみ
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Toray Industries Inc
Original Assignee
Toray Industries Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Toray Industries Inc filed Critical Toray Industries Inc
Priority to JP2021545380A priority Critical patent/JP7067676B1/ja
Priority to CN202180047180.7A priority patent/CN115769145A/zh
Priority to KR1020227037159A priority patent/KR102722567B1/ko
Priority to JP2022004121A priority patent/JP7111267B2/ja
Publication of WO2022030324A1 publication Critical patent/WO2022030324A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

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
    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
    • 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
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • 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
    • H05K3/30—Assembling printed circuits with electric components, e.g. with resistors
    • H05K3/32—Assembling printed circuits with electric components, e.g. with resistors electrically connecting electric components or wires to printed circuits
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
    • H10W95/00—Packaging processes not covered by the other groups of this subclass
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
    • H10W72/00—Interconnections or connectors in packages
    • H10W72/071—Connecting or disconnecting
    • H10W72/072—Connecting or disconnecting of bump connectors
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
    • H10W90/00—Package configurations
    • H10W90/701—Package configurations characterised by the relative positions of pads or connectors relative to package parts
    • H10W90/721—Package configurations characterised by the relative positions of pads or connectors relative to package parts of bump connectors
    • H10W90/724—Package configurations characterised by the relative positions of pads or connectors relative to package parts of bump connectors between a chip and a stacked insulating package substrate, interposer or RDL

Definitions

  • the present invention relates to a conductive paste, a printed wiring board, a method for manufacturing a printed wiring board, and a method for manufacturing a printed circuit board.
  • a conductive photoresist or the like to which conductive fine particles are added is applied to the surface of the printed wiring board, and then exposed and developed to form a conductive bump on the electrode of the printed wiring board. Then, a method of joining the conductive bump and the LED electrode via a conductive adhesive is known (see, for example, Patent Document 1).
  • Patent Document 1 has a problem that the number of processes increases and the production efficiency is poor because a separate adhesive is required to bond the conductive bump and the LED electrode.
  • an object of the present invention is to provide a conductive paste that can mount an LED at a low temperature and a low pressure without using a separate adhesive and can increase the bonding strength between the conductive bump and the LED electrode.
  • the present invention mainly has the following configurations in order to solve the above problems.
  • the conductive paste of the present invention can mount electronic components with high bonding strength at low temperature and low pressure without using a separate adhesive.
  • the conductive paste of the present invention refers to a paste in which conductive particles are dispersed in an organic component, and is a non-photosensitive conductive paste and an organic component used by removing a solvent and thermally curing a resin after coating on a substrate. It also includes a photosensitive conductive paste that can be adjusted to form a pattern by exposure and development processes.
  • the conductive paste of the present invention is a conductive paste containing an organic component and conductive particles, and has a storage elastic modulus G'(P100) of the dried film of the conductive paste at 100 ° C. of 0.01 MPa or less and 140 ° C.
  • the storage elastic modulus G'(C25) at 25 ° C. after heating for 30 minutes is 0.01 MPa or more.
  • the storage elastic modulus G'(P25) of the dried film of the conductive paste at 25 ° C. is 0.1 MPa or more, workability is improved such that shape change due to contact or external pressure during the process can be suppressed. ..
  • the storage elastic modulus G'(P25) at 25 ° C. is 0.00001 to 0.01 MPa
  • the storage elastic modulus G'(P25) at 25 ° C. is 0.1 to 50,000 MPa.
  • the storage elastic modulus G'(C25) at 25 ° C. after heating at 140 ° C. for 30 minutes is 0.01 to 100,000 MPa, both workability and low-temperature mountability can be achieved.
  • the storage elastic modulus G'(P100) of the dry film at 100 ° C. is 1/10 or less of the storage elastic modulus G'(P25) of the dry film at 25 ° C., both workability and low temperature mountability can be further achieved. become.
  • a conductive paste satisfying the above conditions there is a conductive paste containing a carboxyl group-containing polymer, a photopolymerization initiator, an epoxy resin and a novolak type phenol resin as organic components.
  • the conductive paste containing these components can not only further increase the die shear strength after mounting, but also enable the formation of fine bumps by exposing the dry film and developing it. Further, by containing the curing catalyst of the epoxy resin, the curing reaction of the epoxy resin can be promoted, and the die share strength can be further increased.
  • the storage elastic modulus G'(E100) of the film after exposing the dry film of the conductive paste to an i-line (wavelength 365 nm) exposure amount of 500 mJ / cm 2 at 100 ° C. is the storage elastic modulus G'(E25) at 25 ° C. When it is 1/10 or less of, it becomes possible to achieve both fine workability and low temperature mountability.
  • the conductive paste that can form a pattern by exposure and development is a photosensitive conductive paste containing a photosensitive component and conductive particles, and the photosensitive conductive paste is dried at 100 ° C. for 30 minutes.
  • the obtained dry film was exposed to an i-line (wavelength 365 nm) exposure of 500 mJ / cm 2 , and was shower-developed with a 0.1 mass% sodium carbonate aqueous solution for 30 seconds.
  • the storage elastic modulus of the film at 100 ° C. G'(D100) is less than 0.01 MPa
  • the storage elastic modulus G'(C25) at 25 ° C. after heating the developed film at 140 ° C. for 30 minutes is 0.01 MPa or more.
  • the "storage elastic modulus G'(D100)” is the storage elastic modulus G'when the dynamic viscoelasticity measurement (temperature dependence) of the developed film is performed by a rheometer.
  • Dynamic viscoelasticity is a component (elastic component) that matches the phase of the shear stress that appears when a steady state is reached when shear strain is applied to the material at a sine frequency, and the strain and phase are It is a method to analyze the dynamic mechanical properties of a material by decomposing it into a component (viscous component) delayed by 90 °.
  • the storage elastic modulus G' is the stress component whose phase matches the shear strain divided by the shear strain.
  • the storage modulus G' represents the elasticity of the material to dynamic strain at each temperature and is related to the hardness of the film after development. Therefore, the storage elastic modulus G'at each measured temperature affects the following characteristics of the developed film. Specifically, G'(D100) affects the fluidity of the developed film during heating, and G'(C25) affects the bonding strength of the cured film.
  • the bonding strength between the bump formed by using the photosensitive conductive paste and the electronic component bonded to the bump is improved. ..
  • the bump is formed by heating and crimping the electrode portion of the electronic component and the bump while heating at 100 ° C. or higher, so that the bump is formed according to the electrode shape of the electronic component. This is because a high adhesion force can be obtained between the bump and the electrode because it flows and deforms quickly.
  • G'(D100) is more preferably 0.007 MPa or less.
  • the lower limit of G'(D100) is not particularly limited, but if the fluidity of the conductive bumps during heat crimping is too high, short-circuit defects that electrically connect to adjacent electronic components will occur. From the viewpoint of prevention, it is preferably 0.002 MPa or more.
  • the cured film described above has a G'(C25) of 0.01 MPa or more, more preferably 0.05 MPa or more.
  • G'(C25) is not particularly limited, but from the viewpoint of ease of repair when a malfunction of the electronic component is found after joining the electronic component and the printed wiring board, G'(C25) ) Is preferably 1.0 MPa or less.
  • both G'(D100) and G'(C25) are often 0.01 MPa or more.
  • the photopolymerizability described later is added to the paste. Examples thereof include a method of containing a carboxyl group-containing resin having a group and a carboxyl group-containing resin having no photopolymerizable group.
  • the joint strength between the electronic component and the bump can be evaluated by, for example, the die shear strength.
  • the die shear strength is an index showing the joining strength when a force in the horizontal direction (force in the shearing direction) is applied to the joining member joined to the member to be joined.
  • the die shear strength can be measured using a general die shear strength measuring device.
  • the conductive paste of the present invention preferably contains a photosensitive component.
  • a photosensitive component By containing the photosensitive component, it is possible to form fine conductive bumps with high positional accuracy on the electrodes of the printed wiring board.
  • the photosensitive component include a photopolymerization initiator, a compound having an unsaturated double bond, a carboxyl group-containing resin having a photopolymerizable group, and the like.
  • the conductive paste of the present invention preferably contains a photopolymerization initiator.
  • the photopolymerization initiator include benzophenone derivatives, acetophenone derivatives, thioxanthone derivatives, benzyl derivatives, benzoin derivatives, oxime compounds, ⁇ -hydroxyketone compounds, ⁇ -aminoalkylphenone compounds, phosphinoxide compounds, anthrone compounds, and anthraquinones. Examples include compounds.
  • the content of the photopolymerization initiator in the conductive paste of the present invention is preferably 0.05 to 30 parts by weight with respect to 100 parts by weight of the carboxyl group-containing resin having a photopolymerizable group.
  • the content of the photopolymerization initiator is 0.05 parts by weight or more, the curing density of the exposed portion is increased, and the residual film ratio after development can be increased.
  • the content of the photopolymerization initiator is 30 parts by weight or less, the wiring pattern thickening due to excessive light absorption by the photopolymerization initiator on the upper portion of the coating film obtained by applying the photosensitive conductive paste is suppressed and fine. Workability can be further improved.
  • the conductive paste of the present invention preferably contains a compound having an unsaturated double bond.
  • the "compound having an unsaturated double bond” means a monomer having an unsaturated double bond.
  • Examples of the compound having an unsaturated double bond include ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 1.4-butanediol dimethacrylate, neopentyl glycol dimethacrylate, glycerin dimethacrylate, and 2-hydroxyl.
  • the content of the compound having an unsaturated double bond in the conductive paste of the present invention is preferably 1 to 100 parts by weight with respect to 100 parts by weight of the carboxyl group-containing resin having a photopolymerizable group.
  • the content of the compound having an unsaturated double bond is 1 part by weight or more, the crosslink density of the exposed part is increased, and the difference in solubility between the unexposed part and the exposed part in the developing solution can be increased, and fine processing can be performed. The sex can be improved.
  • G'(D100) can be further reduced.
  • the conductive paste of the present invention preferably contains a carboxyl group-containing resin having a photopolymerizable group as a photosensitive component.
  • this resin contains a carboxyl group, the alkali developability can be enhanced and the microfabrication by the photolithography method can be enhanced. Further, since this resin has a photopolymerizable group, it remains as an organic component in the film after development. Therefore, it is possible to suppress the phenomenon that G'(D100) increases due to an increase in the proportion of conductive particles in the film due to a decrease in the film (decrease in organic components) during development.
  • Examples of the carboxyl group-containing resin having a photopolymerizable group include a carboxyl group-containing acrylic copolymer, a carboxylic acid-modified epoxy resin, a carboxylic acid-modified phenol resin, a polyamic acid, and a carboxylic acid-modified siloxane polymer. Two or more of these may be contained. Among these, a carboxyl group-containing acrylic copolymer having a high ultraviolet light transmittance or a carboxylic acid-modified epoxy resin is preferable, and a carboxylic acid-modified epoxy resin is more preferable.
  • carboxyl group-containing acrylic copolymer a copolymer of an acrylic monofunctional monomer and an unsaturated acid or an acid anhydride thereof is preferable.
  • acrylic monofunctional monomer examples include methyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate, n-butyl acrylate, isobutyl acrylate, isopropane acrylate, glycidyl acrylate, butoxytriethylene glycol acrylate, dicyclopentanyl acrylate, and dicyclo.
  • unsaturated acids or acid anhydrides thereof include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, vinyl acetate, and acid anhydrides thereof. Two or more of these may be used.
  • the acid value of the carboxyl group-containing acrylic copolymer can be adjusted by the copolymerization ratio of the unsaturated acid.
  • the carboxylic acid-modified epoxy resin a reaction product of an epoxy compound and an unsaturated acid or an unsaturated acid anhydride is preferable.
  • the carboxylic acid-modified epoxy resin is a carboxylic acid-modified epoxy resin obtained by modifying the epoxy group of an epoxy compound with a carboxylic acid or a carboxylic acid anhydride, and does not contain an epoxy group.
  • Examples of the epoxy compound include glycidyl ethers, glycidyl amines, and epoxy resins. More specifically, examples of the glycidyl ethers include methyl glycidyl ether, ethyl glycidyl ether, butyl glycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, and tripropylene glycol diglycidyl ether.
  • the glycidylamines include tert-butylglycidylamine and the like.
  • the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, novolak type epoxy resin, hydrogenated bisphenol A type epoxy resin and the like. Two or more of these may be used.
  • An unsaturated double bond can be introduced by reacting the above-mentioned carboxyl group-containing acrylic copolymer or carboxylic acid-modified epoxy resin with a compound having an unsaturated double bond such as glycidyl (meth) acrylate. ..
  • a compound having an unsaturated double bond such as glycidyl (meth) acrylate. ..
  • the acid value of the carboxyl group-containing resin having a photopolymerizable group can be adjusted to a desired range by the ratio of the unsaturated acid in the constituent components.
  • a carboxylic acid-modified epoxy resin it can be adjusted to a desired range by reacting with a polybasic acid anhydride.
  • the ratio of the polybasic acid anhydride in the constituents can be adjusted to a desired range.
  • the conductive paste of the present invention preferably contains an epoxy resin.
  • the epoxy resin include bisphenol A type, cresol novolak type, phenol novolak type, bisphenol A novolak type, dicyclopentadiene type, naphthalene type and the like, and among them, those having a softening point of 30 ° C. or higher and 100 ° C. or lower are preferable. .. If the softening point is 30 ° C.
  • EPICRON N-660 softening point 61 to 69 ° C.
  • EPICRON N-670 softening point 68 to 76 ° C.
  • EPICRON N-680 softening point 80 to 90 ° C.
  • EPICRON N-770 softening point 65-75 ° C
  • EPICRON N-775 softening point 70-80 ° C
  • EPICRON N-865 softening point 64-72 ° C
  • EPICRON N-890 softening point 75-90) ° C.
  • EPICRON HP-7200L softening point 50-60 ° C.
  • EPICRON HP-7200 softening point 57-68 ° C.
  • EPICRON HP-7200H softening point 75-90 ° C.
  • EPICRON HP-4700 softening point 85 ° C.) -98 ° C
  • KAYARAD NC-3000 softening point 53-63 ° C) manufactured by Nippon Kayaku Co., Ltd., NC-3000H (softening point 65-75 ° C), and the like. Two or more of these may be used.
  • the conductive paste of the present invention preferably contains a novolak-type phenol resin.
  • the bonding strength between the conductive bump and the electronic component such as the LED electrode can be increased.
  • those having a softening point of 30 ° C. or higher and 100 ° C. or lower are preferable. If the softening point is 30 ° C. or higher, it is possible to suppress the occurrence of short-circuit defects with neighboring bumps due to excessive flow during heat crimping, and if it is 100 ° C. or lower, component mounting at low temperature is possible.
  • KAYARAD GPH-65 softening point 63 to 69 ° C
  • KAYARAD GPH-103 Meiwa Kasei Co., Ltd.
  • H-4 softening point 67 to 75 ° C
  • HF HF manufactured by Nippon Kayaku Co., Ltd.
  • the total amount of the epoxy resin and the novolak-type phenol resin added in the present invention is preferably 1 to 100 parts by weight with respect to 100 parts by weight of the carboxyl group-containing polymer. If the total addition amount of the epoxy resin and the novolak type phenol resin is 1 part by weight or more, the bonding strength between the conductive bump and the electronic component such as the LED electrode can be increased, and if it is 100 parts by weight or less, it is melted during development. It is possible to improve the properties and high-resolution patterning is possible.
  • the ratio of the epoxy resin to the novolak-type phenol resin is preferably adjusted to the ratio of the epoxy equivalent of the epoxy resin to be used and the hydroxyl group equivalent of the novolak-type phenol resin.
  • the conductive paste of the present invention preferably contains a curing accelerator that accelerates the curing of the epoxy resin and the novolak type phenol resin.
  • a curing accelerator that accelerates the curing of the epoxy resin and the novolak type phenol resin.
  • the bonding strength between the conductive bump and the electronic component such as the LED electrode can be increased.
  • imidazoles, dicyandiamide derivatives, quaternary ammonium salts, triphenylphosphine, tetraphenylphosphonium tetraphenylborate can be mentioned. Two or more of these may be used.
  • the amount of the curing accelerator added in the present invention is preferably 0.01 to 5 parts by weight with respect to 100 parts by weight of the epoxy resin. If the amount of the curing accelerator added is 0.01 parts by weight or more, the bonding strength between the conductive bump and the electronic component such as the LED electrode can be increased, and if it is 5 parts by weight or less, the curing reaction is excessive during heat crimping. However, the temperature margin at the time of heat crimping can be widened.
  • the conductive paste of the present invention preferably contains a carboxyl group-containing resin having no photopolymerizable group.
  • a carboxyl group-containing resin having no photopolymerizable group By containing a carboxyl group-containing resin having no photopolymerizable group, it is possible to increase the flexibility of the film after development during heating while maintaining the alkali developability. As a result, it becomes easy to prepare so as to reduce G'(D100) to less than 0.01 MPa while keeping G'(C25) at 0.01 MPa or more.
  • Examples of the carboxyl group-containing resin having no photopolymerizable group include carboxyl group-containing oligomers. More specifically, solid JONCRYL 67 (glass transition point 73 ° C.), JONCRYL 678 (glass transition point 85 ° C.), JONCRYL 611 (glass transition point 50 ° C.), JONCRYL 693 (glass transition point) manufactured by BASF Japan Co., Ltd.
  • those having a glass transition point of 110 ° C. or lower are preferable from the viewpoint of lowering G'(D100). Further, a solid carboxyl group-containing oligomer is preferable.
  • the glass transition point can be measured by differential scanning calorimetry (DSC) using, for example, a differential scanning calorimeter (DSC-60A plus; manufactured by Shimadzu Corporation).
  • DSC differential scanning calorimetry
  • the content of the carboxyl group-containing resin having no photopolymerizable group in the conductive paste of the present invention is preferably 1 to 50 parts by weight with respect to 100 parts by weight of the carboxyl group-containing resin having a photopolymerizable group.
  • the content of the carboxyl group-containing resin having no photopolymerizable group is 1 part by weight or more, the above-mentioned G'(D100) can be further reduced, and the adhesion between the electronic component and the conductive bump is enhanced. , It is possible to improve the bonding strength of the film after curing.
  • the content of the carboxyl group-containing resin having no photopolymerizable group is 50% by weight or less, pattern peeling during development can be suppressed.
  • the content of the carboxyl group-containing resin having no photopolymerizable group is more preferably 5 to 40 parts by weight.
  • the conductive paste of the present invention contains conductive particles.
  • conductive particles include silver, gold, copper, platinum, lead, tin, nickel, aluminum, tungsten, molybdenum, chromium, titanium, indium, magnesium, cobalt, zinc, potassium, lithium, iron, mercury, and berylium.
  • Particles such as cadmium, rhodium, ruthenium, iridium and alloys thereof can be mentioned. Two or more of these may be contained.
  • metal particles selected from silver, gold and copper are preferable from the viewpoint of conductivity, and silver particles are more preferable from the viewpoint of cost and stability.
  • the conductive particles may be those having a surface coated with a resin, an inorganic oxide, or the like.
  • Metallic particles are preferable because the conductive particles having the surface of the resin particles or the inorganic oxide particles coated with metal have elastic repulsion due to the resin particles at the time of mounting.
  • the aspect ratio which is the value obtained by dividing the major axis length of the conductive particles by the minor axis length, is preferably 1.1 to 2.0.
  • SEM scanning electron microscope
  • TEM transmission electron microscope
  • the major axis length and the minor axis length of each can be measured and calculated from the average value of both.
  • the average particle size of the conductive particles is preferably 0.05 to 5.0 ⁇ m.
  • the average particle size of the conductive particles is more preferably 0.1 ⁇ m or more.
  • the average particle diameter of the conductive particles is 5.0 ⁇ m or less, the surface smoothness, pattern accuracy, and dimensional accuracy of the obtained conductive pattern can be improved.
  • the average particle size of the conductive particles is more preferably 2.0 ⁇ m or less.
  • the average particle size of the conductive particles can be measured using a laser irradiation type particle size distribution meter. The value of D50 of the particle size distribution obtained by the measurement is defined as the average particle diameter (D50) of the conductive particles.
  • the content of the conductive particles in the conductive paste of the present invention is preferably 30 to 90% by weight in the total solid content.
  • the content of the conductive particles is more preferably 50% by weight or more.
  • the total solid content means all the constituents of the conductive paste excluding the solvent.
  • the conductive paste of the present invention can contain a solvent.
  • the solvent include N, N-dimethylacetamide (boiling point 165 ° C.), N, N-dimethylformamide (boiling point 153 ° C.), N-methyl-2-pyrrolidone (boiling point 204 ° C.), and dimethylimidazolidinone (boiling point 225 ° C.).
  • a solvent having a solubility in 100 g of water at 20 ° C. or higher and a boiling point of 200 ° C. or higher are preferable.
  • N-methyl-2-pyrrolidone, dimethylimidazolidinone, ⁇ -butyrolactone, diethylene glycol monobutyl ether, and diethylene glycol are preferable.
  • the adhesive strength between the electronic component and the conductive bump can be further improved. Further, when the boiling point is 200 ° C. or higher, the volatilization of the solvent is suppressed, and the thickening of the photosensitive conductive paste can be suppressed.
  • the solvent content in the conductive paste of the present invention is preferably 3 to 30% by weight in the total paste composition.
  • the viscosity of the conductive paste can be set in a range suitable for coating such as printing, and good coatability can be obtained.
  • the conductive paste of the present invention may contain additives such as plasticizers, leveling agents, surfactants, silane coupling agents, defoaming agents and pigments as long as the desired properties are not impaired.
  • plasticizer examples include dibutyl phthalate, dioctyl phthalate, polyethylene glycol, glycerin and the like.
  • leveling agent examples include a special vinyl-based polymer and a special acrylic-based polymer.
  • silane coupling agent examples include methyltrimethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, hexamethyldisilazane, 3-methacryloxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and vinyltri. Examples include methoxysilane.
  • the printed wiring board of the present invention includes a dried film of the conductive paste of the present invention or a film after the dried film is exposed and developed. As a result, it becomes soft at the time of heating and is cured after heating, so that the bonding strength with the electronic component after curing can be increased without using a separate adhesive when bonding the electronic component.
  • the conductive paste of the present invention includes a thermosetting resin component such as an epoxy resin or a novolak-type phenol resin, a photopolymerization initiator that reacts with exposure light, a compound having an unsaturated double bond, a carboxyl group-containing polymer, and photopolymerization. It can be produced by mixing conductive particles in an organic substance in which a carboxyl group-containing resin having no sex group, a solvent, and an additive are appropriately mixed. Examples of the mixing device include a disperser such as a three-roller mill, a ball mill, and a planetary ball mill, and a kneader.
  • a disperser such as a three-roller mill, a ball mill, and a planetary ball mill, and a kneader.
  • One of the methods for manufacturing a printed circuit board of the present invention is a step of forming a dry film of the conductive paste of the present invention on a printed wiring board, and exposing and developing the dry film on an electrode of the printed wiring board. It has a step of forming a conductive bump and a step of heat-pressing an electronic component having an electrode on the conductive bump.
  • FIG. 1 is a process diagram showing an example of a method for manufacturing a printed circuit board of the present invention.
  • the dry film 1 of the conductive paste of the present invention is formed on the printed wiring board 2.
  • a coating method for example, rotary coating using a spinner, spray coating, roll coating, screen printing, blade coater, die coater, calendar Application using a coater, a meniscus coater or a bar coater can be mentioned.
  • the film thickness of the dry film of the photosensitive conductive paste is preferably 1 to 10 ⁇ m.
  • the film thickness of the dry film is more preferably 2 to 5 ⁇ m.
  • the film thickness of the dried film of the photosensitive conductive paste can be measured using, for example, a stylus type step meter such as "Surfcom (registered trademark)" 1400 (manufactured by Tokyo Precision Co., Ltd.). More specifically, the film thicknesses at three random positions are measured with a stylus type step meter (measurement length: 1 mm, scanning speed: 0.3 mm / sec), and the average value is taken as the film thickness.
  • a stylus type step meter such as "Surfcom (registered trademark)” 1400 (manufactured by Tokyo Precision Co., Ltd.). More specifically, the film thicknesses at three random positions are measured with a stylus type step meter (measurement length: 1 mm, scanning speed: 0.3 mm / sec), and the average value is taken as the film thickness.
  • drying method examples include heat drying using an oven, a hot plate, infrared rays, and vacuum drying.
  • the drying temperature is preferably 50 to 180 ° C.
  • the drying time is preferably 1 minute to several hours.
  • the dry film 1 is exposed and developed to form a conductive bump 4 on the electrode 3 of the printed wiring board 2.
  • a light source that emits i-line (wavelength 365 nm), h-line (wavelength 405 nm) or g-line (wavelength 436 nm) such as a high-pressure mercury lamp, an ultra-high pressure mercury lamp, and an LED is used, and vacuum adsorption exposure and proxy exposure are used.
  • i-line wavelength 365 nm
  • h-line wavelength 405 nm
  • g-line wavelength 436 nm
  • Projection exposure direct drawing exposure and various other exposure methods.
  • the illuminance ratio of the exposure light at the time of exposure is preferably 1.1 to 1.9.
  • the illuminance ratio is 1.1 or more, excessive photoreaction does not occur, electronic parts can be heat-bonded under low-temperature and low-pressure conditions, and when the illuminance ratio is 1.9 or less, the photoreaction of the exposed part is efficient. It is possible to widen the process margin during development.
  • Examples of the developing method include a method of spraying a developer onto the dry film surface while allowing or rotating a substrate having a dried film of exposed photosensitive conductive paste, and a substrate having a dried film of exposed photosensitive conductive paste. Examples thereof include a method of immersing in a developing solution and a method of applying ultrasonic waves while immersing a substrate having a dry film of exposed photosensitive conductive paste in a developing solution.
  • the developing solution is preferably an alkaline aqueous solution, for example, tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethyl acetate.
  • alkaline aqueous solution for example, tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethyl acetate.
  • alkaline aqueous solution for example, tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethyl acetate.
  • polar solvents such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, and ⁇ -butyrolactone; methanol, ethanol, isopropanol, etc. may be added to these aqueous solutions.
  • Alcohols such as ethyl lactate and propylene glycol monomethyl ether acetate; Ketones such as cyclopentanone, cyclohexanone, isobutyl ketone and methyl isobutyl ketone;
  • One or more surfactants may be added.
  • rinsing treatment with a rinsing liquid may be performed.
  • the rinsing solution include water or an aqueous solution obtained by adding alcohols such as ethanol and isopropyl alcohol or esters such as ethyl lactate and propylene glycol monomethyl ether acetate to water.
  • the electronic component 5 having the electrode 6 is heat-bonded onto the conductive bump 4.
  • the heating temperature is preferably 60 ° C. or higher and 250 ° C. or lower, and more preferably 60 ° C. or higher and 160 ° C. or lower.
  • Photosensitive conductive paste design to increase the difference between the storage elastic modulus G'of the conductive bump at room temperature and the storage elastic modulus G'of the conductive bump at the time of mounting by raising the heating temperature to 60 ° C. or higher. It will be easy. Further, by setting the heating temperature to 250 ° C. or lower, the thermal expansion and contraction of the printed wiring board and the electronic component can be reduced, so that the position accuracy of the mounting can be further improved.
  • a heat crimping tool for a flip chip bonder, a vacuum diaphragm type laminator, or the like can be used.
  • the pattern may be irradiated with ultrasonic waves during heat crimping. By irradiating ultrasonic waves, the bonding strength of the film after curing between the conductive bump and each electrode can be further improved.
  • the pattern may be irradiated with a laser during heat crimping. By irradiating the laser, the sintering of the conductive bumps proceeds in a short time, and the production efficiency can be improved.
  • the laser light source is not particularly limited, but can be appropriately adopted depending on the wavelength matched to the absorption band of the metal.
  • laser light sources include solid-state lasers (ruby, glass, YAG, etc.), semiconductor lasers (GaAs, InGaAsP, etc.), liquid lasers (dye, etc.), and gas lasers (He-Ne, Ar, CO 2 , excimer, etc.). Can be mentioned.
  • Examples of electronic components include chip-type electronic components such as LED chips having at least one connection terminal, MiniLED chips, ⁇ LED chips, IC chips, LSI chips, resistance chips, and capacitor chips.
  • the printed circuit board on which ⁇ LED is mounted has excellent display characteristics such as high brightness, power saving, and high response speed.
  • the surface of the electrode of the electronic component having the electrode has an unevenness of 0.5 ⁇ m or more. By having the unevenness of 0.5 ⁇ m or more, the uneven portion bites into the conductive bump at the time of mounting, high adhesion is obtained, and the bonding strength of the film after curing is improved.
  • One of the methods for manufacturing a printed circuit board of the present invention is a step of forming a dry film of the conductive paste of the present invention on a surface on which an electrode of an electronic component having an electrode exists, and exposing and exposing the dry film. It has a step of developing and forming a conductive bump on the electrode of the electronic component having the electrode, and a step of heating and crimping the electronic component having the electrode on the conductive bump.
  • FIG. 2 is a process diagram showing an example of the method for manufacturing the printed circuit board of the present invention.
  • the dry film 1 of the conductive paste of the present invention is formed on the surface of the electronic component 5 having the electrodes where the electrodes 6 are present.
  • the same method as the above-mentioned method can be used.
  • the dry film 1 is exposed and developed to form a conductive bump 4 on the electrode 6 of the electronic component 5 having the electrode 6.
  • a method for forming the conductive bump the same method as the above-mentioned method can be used.
  • the conductive bump 4 is heat-bonded onto the electrode 3 of the printed wiring board 2.
  • the same method as the above-mentioned method can be used.
  • the evaluation method in each example is as follows.
  • the conductive pastes obtained in Examples 1 to 21 and Comparative Example 1 were applied onto a glass substrate having a film thickness of 1 mm so that the film thickness after drying was 4 ⁇ m, and the coating film was placed in a drying oven at a temperature of 100 ° C. After drying for 10 minutes on a glass substrate, a dry film was formed, and the storage elastic moduli at 25 ° C. and 100 ° C. were measured using the following devices.
  • Measuring device Triboinder TI950 (manufactured by Hysiron) Measurement method: Nano indentation method Measurement mode: Continuous synthetic measurement method Measurement frequency 100 Hz Indenter used: Sapphire triangular weight indenter (Berkovich indenter) Measurement temperature: 25 ° C, 100 ° C.
  • ⁇ Measurement method (2) of storage elastic modulus G'(E25) and G'(E100) of post-exposure film> The photosensitive conductive pastes obtained in Examples 3 to 21 and Comparative Example 1 were applied onto a glass substrate having a thickness of 1 mm so that the dried film had a thickness of 4 ⁇ m, and the coated film was dried at a temperature of 100 ° C. After drying in an oven for 10 minutes to obtain a dry film, further exposure with an i-line (wavelength 365 nm) exposure amount of 500 mJ / cm 2 was performed to form an exposure film on a glass substrate, and the following device was used. The storage elasticity at 25 ° C and 100 ° C was measured, respectively.
  • Measuring device Triboinder TI950 (manufactured by Hysiron) Measurement method: Nano indentation method Measurement mode: Continuous synthetic measurement method Measurement frequency 100 Hz Indenter used: Sapphire triangular weight indenter (Berkovich indenter) Measurement temperature: 25 ° C, 100 ° C.
  • the mixture was shower-developed for 30 seconds using a 0.1 wt% Na 2 CO 3 aqueous solution, and rinsed with ultrapure water. Then, the developed film was peeled off, cut into a circle having a diameter of 18 mm, and the storage elastic modulus G'(D100) of the developed film was measured using the following apparatus.
  • the conductive pastes obtained in Examples 1 to 21 and Comparative Example 1 were applied to the mold release surface of the PET film "Therapeutic" having a film thickness of 75 ⁇ m so that the film thickness after drying was 50 ⁇ m.
  • the developed film was heated in a drying oven at a temperature of 140 ° C. for 30 minutes to form a cure film.
  • the cure film was peeled off, cut into a circle having a diameter of 18 mm, and the storage elastic modulus G'(C25) of the cure film at 25 ° C. was measured using the following apparatus.
  • Measuring device Viscosity / viscoelasticity measuring device HAAKE MARSIII (manufactured by Thermo Fisher SCIENTIFIC) Measurement conditions: OSC temperature-dependent measurement Geometry: Parallel disk type (20 mm) Angular frequency: 1Hz Angular velocity: 6.2832 rad / sec Temperature range: 25 to 150 ° C (set to 25 ° C when measuring the storage elastic modulus of the developed film) Temperature rise rate: 0.08333 ° C / sec (set only when measuring the storage elastic modulus of the cure film) Sample shape: Circular (diameter 18 mm) Sample thickness: 50 ⁇ m.
  • ⁇ Measurement method of die share strength> The conductive paste obtained in Examples 1 and 2 is applied on a glass substrate by screen printing so that the film thickness after drying is 3 ⁇ m, and the coating film is dried in a drying oven at a temperature of 100 ° C. for 10 minutes. Then, a dry film was formed on the glass substrate.
  • a wafer chip obtained by cutting a 0.7 mm thick silicon wafer into 2 mm squares was placed on a conductive film, mounted using a vacuum diaphragm type laminator (MVLP500 / 600; manufactured by Meiki Seisakusho Co., Ltd.), and then mounted.
  • the sample was heated in a drying oven at a temperature of 140 ° C. for 30 minutes to obtain a sample for measuring the die shear intensity shown in FIG.
  • the mounting conditions were a temperature of 120 ° C., a pressurizing pressure of 1 MPa, and a pressurizing time of 60 seconds.
  • the die shear strength was measured using a die shear strength measuring device (Dage series 4000; manufactured by Dage). The measurement was performed at 25 ° C. and a shear rate of 200 ⁇ m / sec.
  • the photosensitive conductive pastes obtained in Examples 3 to 21 and Comparative Example 1 were coated on a glass substrate by screen printing so that the film thickness after drying was 3 ⁇ m, and the coated film was dried at a temperature of 100 ° C. It was dried in an oven for 10 minutes to form a dry film on a glass substrate.
  • the film was shower-developed for 30 seconds with a 0.1 wt% Na 2 CO 3 aqueous solution and rinsed with ultrapure water to form a conductive film on a glass substrate.
  • a wafer chip obtained by cutting a 0.7 mm thick silicon wafer into 2 mm squares was placed on a conductive film, mounted using a vacuum diaphragm type laminator (MVLP500 / 600; manufactured by Meiki Seisakusho Co., Ltd.), and then mounted.
  • the sample was heated in a drying oven at a temperature of 140 ° C. for 30 minutes to obtain a sample for measuring the die shear intensity shown in FIG.
  • the mounting conditions were a temperature of 120 ° C., a pressurizing pressure of 1 MPa, and a pressurizing time of 60 seconds.
  • the die shear strength was measured using a die shear strength measuring device (Dage series 4000; manufactured by Dage). The measurement was performed at 25 ° C. and a shear rate of 200 ⁇ m / sec.
  • FIG. 3 is a schematic cross-sectional view of a sample for measuring die shear strength.
  • the wafer chip 10 is bonded to the conductive film 9 formed on the glass substrate 8.
  • ⁇ Measurement method of mountable temperature> The conductive pastes of Examples 1 and 2 are applied on a glass substrate by screen printing so that the film thickness after drying is 3 ⁇ m, and the coating film is dried in a drying oven at a temperature of 100 ° C. for 10 minutes to make glass. A dry film was formed on the substrate.
  • a wafer chip obtained by cutting a 0.7 mm thick silicon wafer into 2 mm squares was placed on a dry film and mounted using a vacuum diaphragm type laminator (MVLP500 / 600; manufactured by Meiki Seisakusho Co., Ltd.).
  • MVLP500 / 600 manufactured by Meiki Seisakusho Co., Ltd.
  • a sample for measuring the die shear strength shown in the above was obtained.
  • the mounting conditions were a pressurizing pressure of 1 MPa and a pressurizing time of 60 seconds, and the heating temperatures were 70 ° C., 80 ° C., 90 ° C., 100 ° C., 110 ° C., and 120 ° C.
  • the obtained substrate was heated in a drying oven at a temperature of 140 ° C.
  • the die shear strength was measured using a die shear strength measuring device (Dage series 4000; manufactured by Dage). The measurement was performed at 25 ° C. and a shear rate of 200 ⁇ m / sec. The minimum heating temperature at which the value of the die shear strength was 5 N / mm 2 or more was set as the mountable temperature.
  • the photosensitive conductive pastes obtained in Examples 3 to 21 and Comparative Example 1 were applied by screen printing so that the film thickness after drying was 3 ⁇ m, and the coating film was applied in a drying oven at a temperature of 100 ° C. for 10 minutes. It was dried to form a dry film on a glass substrate.
  • the film was shower-developed for 30 seconds using a 0.1 wt% Na 2 CO 3 aqueous solution, rinsed with ultrapure water, and a post-development film was formed on a glass substrate.
  • a wafer chip obtained by cutting a 0.7 mm thick silicon wafer into 2 mm squares was placed on a film after development, and mounted using a vacuum diaphragm type laminator (MVLP500 / 600; manufactured by Meiki Seisakusho Co., Ltd.).
  • the sample for measuring the die shear strength shown in 3 was obtained.
  • the mounting conditions were a pressurizing pressure of 1 MPa and a pressurizing time of 60 seconds, and the heating temperatures were 70 ° C., 80 ° C., 90 ° C., 100 ° C., 110 ° C., and 120 ° C.
  • the obtained substrate was heated in a drying oven at a temperature of 140 ° C.
  • the die shear strength was measured using a die shear strength measuring device (Dage series 4000; manufactured by Dage). The measurement was performed at 25 ° C. and a shear rate of 200 ⁇ m / sec. The minimum heating temperature at which the value of the die shear strength was 5 N / mm 2 or more was set as the mountable temperature.
  • Photosensitive component Carboxyl group-containing acrylic copolymer having an unsaturated double bond (A) 150 g of diethylene glycol monobutyl ether (hereinafter referred to as “DGME”) was charged in a reaction vessel having a nitrogen atmosphere, and the temperature was raised to 80 ° C. using an oil bath.
  • DGME diethylene glycol monobutyl ether
  • EA ethyl acrylate
  • 2-EHMA 2-ethylhexyl methacrylate
  • BA n-butyl acrylate
  • MAA trimethylolacrylamide
  • MAA trimethylolacrylamide
  • BP-4EA [Compound with unsaturated double bond] -"Light Acrylate (registered trademark)" BP-4EA (manufactured by Kyoeisha Chemical Co., Ltd.) (hereinafter referred to as BP-4EA).
  • [Conductive particles] -Ag particles with a particle diameter (D50) of 0.7 ⁇ m and an aspect ratio of 1.1 (hereinafter referred to as Ag particles).
  • Resin core Ag-coated particles having a particle diameter (D50) of 0.7 ⁇ m and an aspect ratio of 1.1 average particle diameter of resin core particles of 0.65 ⁇ m).
  • H-4 [Novolak type phenolic resin] -Standard type H-4 (manufactured by Meiwa Kasei Co., Ltd.) (hereinafter referred to as H-4), hydroxyl group equivalent 105 g / eq, softening point 72 ° C. -High heat resistance, high rigidity type MEH-7600-4H (manufactured by Meiwa Kasei Co., Ltd.) (hereinafter referred to as MEH-7600), hydroxyl group equivalent 100 g / eq, softening point 155 ° C.
  • C11Z-A [Curing accelerator] -"Curesol (registered trademark)" C11Z-A (manufactured by Shikoku Kasei Co., Ltd.) (hereinafter referred to as C11Z-A).
  • Example 1 In a 100 mL clean bottle, put 15 g of "840", 8.51 g of H-4, 5 g of JONCRYL 67, and 6 g of DGME, and rotate-revolve vacuum mixer "Awatori Rentaro (registered trademark)" ARE-310 (((registered trademark)) (Manufactured by Shinky Co., Ltd.) was used for mixing to obtain 34.51 g of a resin solution.
  • Example 2 In a 100 mL clean bottle, put 15 g of "840", 8.51 g of H-4, 5 g of JONCRYL 67, 1.18 g of C11Z-A, and 6 g of DGME, and rotate-revolve vacuum mixer "Awatori Rentaro (registered). Mixing was performed using "ARE-310 (manufactured by Shinky Co., Ltd.)" to obtain 35.69 g of a resin solution.
  • ARE-310 manufactured by Shinky Co., Ltd.
  • Example 3 Carboxyl group-containing acrylic copolymer (A) with 13.59 g unsaturated double bond, 4.08 g JONCRYL 67, 0.60 g OXE04, 2.00 g BP-4EA, 5 in a 100 mL clean bottle. .66 g of DGME was added and mixed using a rotation-revolution vacuum mixer "Awatori Rentaro (registered trademark)" ARE-310 (manufactured by Shinky Co., Ltd.) to obtain 25.93 g of a resin solution.
  • each storage elastic modulus G', mountable temperature, and die shear strength were evaluated by the above-mentioned methods.
  • the evaluation results are shown in Table 2.
  • Example 4 A photosensitive conductive paste having the composition shown in Table 1 was prepared by the same method as in Example 1, and evaluated in the same manner as in Example 3. The evaluation results are shown in Table 2.
  • Example 11 In a 100 mL clean bottle, a carboxyl group-containing acrylic copolymer (A) having a 13.59 g unsaturated double bond, 0.68 JONCRYL 819, 0.60 g OXE04, 2.00 g BP-4EA, 4 .93 g of DGME was added and mixed using a rotation-revolution vacuum mixer "Awatori Rentaro (registered trademark)" ARE-310 (manufactured by Shinky Co., Ltd.) to obtain 21.80 g of a resin solution.
  • A carboxyl group-containing acrylic copolymer having a 13.59 g unsaturated double bond, 0.68 JONCRYL 819, 0.60 g OXE04, 2.00 g BP-4EA, 4 .93 g of DGME was added and mixed using a rotation-revolution vacuum mixer "Awatori Rentaro (registered trademark)" ARE-310 (manufactured by Shinky Co., Ltd.) to obtain 21
  • Example 12 In a 100 mL clean bottle, a carboxyl group-containing acrylic copolymer (A) having a 13.59 g unsaturated double bond, 2.04 g of JONCRYL 819, 0.60 g of OXE04, 2.00 g of BP-4EA, 5 .23 g of DGME was added and mixed using a rotation-revolution vacuum mixer "Awatori Rentaro (registered trademark)" ARE-310 (manufactured by Shinky Co., Ltd.) to obtain 23.46 g of a resin solution.
  • A carboxyl group-containing acrylic copolymer having a 13.59 g unsaturated double bond
  • 2.04 g of JONCRYL 819 0.60 g of OXE04, 2.00 g of BP-4EA, 5 .23 g of DGME was added and mixed using a rotation-revolution vacuum mixer "Awatori Rentaro (registered trademark)" ARE-310 (manufactured by Shin
  • Example 13 Carboxyl group-containing acrylic copolymer (A) with 13.59 g unsaturated double bond, 4.08 JONCRYL 819, 0.60 g OXE04, 2.00 g BP-4EA, 5 in a 100 mL clean bottle.
  • Example 14 The exposure conditions of Example 13 were adjusted so that when the i-line (wavelength 365 nm) exposure amount was 500 mJ / cm 2 using an optical filter, the h-line (wavelength 405 nm) exposure amount was 2000 mJ / cm 2 . Evaluation was performed in the same manner as in Example 3. The evaluation results are shown in Table 2. By adjusting the spectral characteristics as described above, the exposed part can be appropriately photo-reacted, the storage elastic modulus G'(D100) of the developed film can be suppressed to a low level, the mountability can be improved, and the mountable temperature can be lowered. did it.
  • Example 15 In a 100 ml clean bottle, 15.00 g of a carboxyl group-containing acrylic copolymer (A) having an unsaturated double bond, 0.66 g of OXE04, 3.82 g of "840", 2.17 g of H-4, 1.53 g of DGME was added and mixed using a rotation-revolution vacuum mixer "Awatori Rentaro (registered trademark)" ARE-310 (manufactured by Shinky Co., Ltd.) to obtain 23.18 g of a resin solution.
  • the obtained 23.18 g of the resin solution is mixed with 50.52 g of Ag particles having a particle diameter (D50) of 0.7 ⁇ m and an aspect ratio of 1.1, and a three-roller mill (EXAKT M-50; manufactured by EXAKT) is used.
  • the mixture was kneaded using the mixture to obtain 73.70 g of a photosensitive conductive paste.
  • evaluation was performed in the same manner as in Example 3. The evaluation results are shown in Table 2.
  • Example 16 to 21 A photosensitive conductive paste having the composition shown in Table 1 was prepared by the same method as in Example 1, and evaluated in the same manner as in Example 3. The evaluation results are shown in Table 2.
  • the obtained 20.96 g resin solution is mixed with 48.97 g of Ag particles having a particle diameter (D50) of 0.7 ⁇ m and an aspect ratio of 1.1, and a three-roller mill (EXAKT M-50; manufactured by EXAKT) is used.
  • the mixture was kneaded using the mixture to obtain 69.93 g of a photosensitive conductive paste.
  • evaluation was performed in the same manner as in Example 3. The evaluation results are shown in Table 2.
  • the storage elastic modulus G'(P100) of the dry films of Examples 1 to 21 at 100 ° C. is 0.01 MPa or less, the adhesive force between the conductive film and the wafer chip during heat crimping is improved, and after curing.
  • the die shear strength was good at 6.0 N / mm 2 or more.
  • the die share strength was lowered due to the influence of using a carboxyl group-containing resin having a relatively high glass transition point as a carboxyl group-containing resin having no photopolymerizable group, but it was within the permissible range.
  • the G'(D100) of the developed film of Examples 3 to 21 is less than 0.01 MPa, the adhesion between the conductive film and the wafer chip during heat crimping is improved, and the film is bonded after curing. As a result of the improvement in strength, the die shear strength was good at 6.0 N / mm 2 or more.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Organic Chemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Dispersion Chemistry (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Conductive Materials (AREA)
  • Materials For Photolithography (AREA)
  • Electric Connection Of Electric Components To Printed Circuits (AREA)
  • Parts Printed On Printed Circuit Boards (AREA)
  • Adhesives Or Adhesive Processes (AREA)
PCT/JP2021/027862 2020-08-07 2021-07-28 導電ペースト、プリント配線板、プリント配線板の製造方法、プリント回路板の製造方法 Ceased WO2022030324A1 (ja)

Priority Applications (4)

Application Number Priority Date Filing Date Title
JP2021545380A JP7067676B1 (ja) 2020-08-07 2021-07-28 導電ペースト、プリント配線板、プリント配線板の製造方法、プリント回路板の製造方法
CN202180047180.7A CN115769145A (zh) 2020-08-07 2021-07-28 导电糊剂、印刷布线板、印刷布线板的制造方法、印刷电路板的制造方法
KR1020227037159A KR102722567B1 (ko) 2020-08-07 2021-07-28 도전 페이스트, 프린트 배선판, 프린트 배선판의 제조방법, 프린트 회로판의 제조방법
JP2022004121A JP7111267B2 (ja) 2020-08-07 2022-01-14 プリント回路板の製造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2020-134395 2020-08-07
JP2020134395 2020-08-07

Publications (1)

Publication Number Publication Date
WO2022030324A1 true WO2022030324A1 (ja) 2022-02-10

Family

ID=80117408

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2021/027862 Ceased WO2022030324A1 (ja) 2020-08-07 2021-07-28 導電ペースト、プリント配線板、プリント配線板の製造方法、プリント回路板の製造方法

Country Status (5)

Country Link
JP (2) JP7067676B1 (https=)
KR (1) KR102722567B1 (https=)
CN (1) CN115769145A (https=)
TW (1) TWI857240B (https=)
WO (1) WO2022030324A1 (https=)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20260018774A (ko) 2023-06-05 2026-02-09 도레이 카부시키가이샤 감광성 도전 조성물, 그것을 사용한 적층체, 감광성 도전 접착제, 패턴이 형성된 기판의 제조 방법 및 디스플레이 기판

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008089921A (ja) * 2006-09-29 2008-04-17 Toyo Gosei Kogyo Kk 感光性組成物及び高分子複合体
JP2011116968A (ja) * 2009-10-30 2011-06-16 Hitachi Chem Co Ltd 感光性接着剤組成物、並びにそれを用いたフィルム状接着剤、接着シート、接着剤パターン、接着剤層付半導体ウェハ、接着剤層付透明基板、及び半導体装置。
WO2019073926A1 (ja) * 2017-10-11 2019-04-18 東レ株式会社 感光性導電ペーストおよび導電パターン形成用フィルム
WO2019202889A1 (ja) * 2018-04-19 2019-10-24 東レ株式会社 感光性導電ペーストおよびそれを用いたパターン形成グリーンシートの製造方法

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012172128A (ja) * 2011-02-24 2012-09-10 Kuraray Co Ltd 異方導電性接着フィルム
US9464198B2 (en) * 2013-01-30 2016-10-11 Dic Corporation Conductive paste, method for forming conductive pattern, and object with printed conductive pattern
JP6396189B2 (ja) * 2014-11-27 2018-09-26 日東電工株式会社 導電性フィルム状接着剤、フィルム状接着剤付きダイシングテープ及び半導体装置の製造方法
WO2016171083A1 (ja) * 2015-04-21 2016-10-27 東レ株式会社 導電パターン形成部材の製造方法
KR102433526B1 (ko) * 2017-03-28 2022-08-17 도요보 가부시키가이샤 카르복실산 기 함유 폴리에스테르계 접착제 조성물
TWI713845B (zh) * 2017-08-07 2020-12-21 日商拓自達電線股份有限公司 導電性接著劑
KR102632465B1 (ko) * 2018-03-29 2024-02-02 미쯔비시 케미컬 주식회사 점착 시트, 그것을 이용한 도전 부재 적층체, 및, 화상 표시 장치
JP2020092159A (ja) 2018-12-05 2020-06-11 株式会社ブイ・テクノロジー マイクロｌｅｄ実装構造、マイクロｌｅｄディスプレイ及びマイクロｌｅｄディスプレイの製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008089921A (ja) * 2006-09-29 2008-04-17 Toyo Gosei Kogyo Kk 感光性組成物及び高分子複合体
JP2011116968A (ja) * 2009-10-30 2011-06-16 Hitachi Chem Co Ltd 感光性接着剤組成物、並びにそれを用いたフィルム状接着剤、接着シート、接着剤パターン、接着剤層付半導体ウェハ、接着剤層付透明基板、及び半導体装置。
WO2019073926A1 (ja) * 2017-10-11 2019-04-18 東レ株式会社 感光性導電ペーストおよび導電パターン形成用フィルム
WO2019202889A1 (ja) * 2018-04-19 2019-10-24 東レ株式会社 感光性導電ペーストおよびそれを用いたパターン形成グリーンシートの製造方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20260018774A (ko) 2023-06-05 2026-02-09 도레이 카부시키가이샤 감광성 도전 조성물, 그것을 사용한 적층체, 감광성 도전 접착제, 패턴이 형성된 기판의 제조 방법 및 디스플레이 기판

Also Published As

Publication number Publication date
KR102722567B1 (ko) 2024-10-29
JPWO2022030324A1 (https=) 2022-02-10
TW202223539A (zh) 2022-06-16
TWI857240B (zh) 2024-10-01
KR20230048623A (ko) 2023-04-11
JP2022068144A (ja) 2022-05-09
JP7111267B2 (ja) 2022-08-02
CN115769145A (zh) 2023-03-07
JP7067676B1 (ja) 2022-05-16

Similar Documents

Publication Publication Date Title
CN106462068B (zh) 感光性树脂组合物以及电路图案的形成方法
CN1764350A (zh) 树脂掩膜层的除去方法和带焊锡突起的基板的制造方法
TW201009500A (en) Photopolymer composition, solder resist composition for print circuit boards and print circuit boards
CN107430336A (zh) 导电图案形成部件的制造方法
JP7067676B1 (ja) 導電ペースト、プリント配線板、プリント配線板の製造方法、プリント回路板の製造方法
CN104345555B (zh) 焊料凸点形成用树脂组合物、焊料凸点形成方法和具备焊料凸点的构件
JP5884477B2 (ja) 半導体装置の製造方法、それにより得られる半導体装置及びそれに用いる熱硬化性樹脂組成物
CN1849854A (zh) 绝缘图案及其形成方法
CN1908816B (zh) 镀制造型物制造用正型感放射线性树脂组合物、转印膜以及镀制造型物的制造方法
WO2015046018A1 (ja) 感光性遮光ペースト及びタッチセンサー用積層パターンの製造方法
TWI426346B (zh) A photohardenable thermosetting one of the liquid solder resist compositions and a printed circuit board using the same
JPWO2007026520A1 (ja) 感放射線性樹脂組成物およびメッキ造形物の製造方法
CN1088319C (zh) 厚膜导体电路及其制造方法
CN105793804A (zh) 接触式传感器用构件的制造方法和接触式传感器用构件
CN1556159A (zh) 积层电路板用液态感光绝缘油墨
WO2023106177A1 (ja) Ｌｅｄ実装基板の製造方法
JP2025165434A (ja) 電子部品の製造方法および樹脂組成物
JP7722181B2 (ja) 電子部品実装基板およびディスプレイ
JP6717439B1 (ja) 積層部材
JP2022151702A (ja) 回路基板、積層回路基板およびウェアラブルデバイス
JP2021152988A (ja) 導電ペースト、導電パターン形成用フィルム、積層部材及びタッチパネル
JP2025004403A (ja) 感光性導電ペーストおよびそれを用いた導電パターン付き基板
WO2024004652A1 (ja) バンプ付き構造物の製造方法およびバンプパターンを有する基板
JPS5993773A (ja) ビニルエステル接着剤
WO2024252967A1 (ja) 感光性導電組成物、それを用いた積層体、感光性導電接着剤、パターン付き基板の製造方法およびディスプレイ基板

Legal Events

Date Code Title Description
ENP Entry into the national phase

Ref document number: 2021545380

Country of ref document: JP

Kind code of ref document: A

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 21853593

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 21853593

Country of ref document: EP

Kind code of ref document: A1