WO2014175196A1 - ソルダーレジスト組成物およびそれを用いたプリント配線板 - Google Patents
ソルダーレジスト組成物およびそれを用いたプリント配線板 Download PDFInfo
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- WO2014175196A1 WO2014175196A1 PCT/JP2014/061100 JP2014061100W WO2014175196A1 WO 2014175196 A1 WO2014175196 A1 WO 2014175196A1 JP 2014061100 W JP2014061100 W JP 2014061100W WO 2014175196 A1 WO2014175196 A1 WO 2014175196A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L97/00—Compositions of lignin-containing materials
- C08L97/02—Lignocellulosic material, e.g. wood, straw or bagasse
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27N—MANUFACTURE BY DRY PROCESSES OF ARTICLES, WITH OR WITHOUT ORGANIC BINDING AGENTS, MADE FROM PARTICLES OR FIBRES CONSISTING OF WOOD OR OTHER LIGNOCELLULOSIC OR LIKE ORGANIC MATERIAL
- B27N3/00—Manufacture of substantially flat articles, e.g. boards, from particles or fibres
- B27N3/04—Manufacture of substantially flat articles, e.g. boards, from particles or fibres from fibres
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H8/00—Macromolecular compounds derived from lignocellulosic materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/02—Cellulose; Modified cellulose
-
- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D101/00—Coating compositions based on cellulose, modified cellulose, or cellulose derivatives
- C09D101/02—Cellulose; Modified cellulose
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D197/00—Coating compositions based on lignin-containing materials
- C09D197/02—Lignocellulosic material, e.g. wood, straw or bagasse
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- 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
- G03F7/0046—Photosensitive materials with perfluoro compounds, e.g. for dry lithography
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- 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
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- 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
- G03F7/0325—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polysaccharides, e.g. cellulose
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- 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
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- 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
- G03F7/075—Silicon-containing compounds
- G03F7/0755—Non-macromolecular compounds containing Si-O, Si-C or Si-N bonds
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- 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 resistor
- H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
- H05K3/34—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by soldering
- H05K3/3452—Solder masks
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27N—MANUFACTURE BY DRY PROCESSES OF ARTICLES, WITH OR WITHOUT ORGANIC BINDING AGENTS, MADE FROM PARTICLES OR FIBRES CONSISTING OF WOOD OR OTHER LIGNOCELLULOSIC OR LIKE ORGANIC MATERIAL
- B27N3/00—Manufacture of substantially flat articles, e.g. boards, from particles or fibres
- B27N3/002—Manufacture of substantially flat articles, e.g. boards, from particles or fibres characterised by the type of binder
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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- 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
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
- H05K1/0366—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement reinforced, e.g. by fibres, fabrics
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- 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
Definitions
- the present invention relates to a solder resist composition and a printed wiring board using the same.
- a printed wiring board is a circuit board with a conductor circuit pattern formed on it. Electronic parts are mounted on the land part of the conductor circuit by soldering, and a solder resist film is used for conductor protection on the circuit part other than the land part. Is coated for. Such a solder resist film has a function of preventing solder from adhering to unnecessary portions and also preventing circuit oxidation and corrosion when an electronic component is mounted on a printed wiring board.
- Patent Document 1 discloses (A) a polymer having a carboxyl group, (B) a photopolymerizable compound having an ethylenically unsaturated bond, and (C) a photopolymerization initiator. And (D) an epoxy resin-encapsulated microcapsule, a photosensitive resin composition is disclosed, but with the increase in performance required for printed wiring boards, realization of a better solder resist is required. .
- JP 2010-128317 A (Claims etc.)
- the first object of the present invention is a good covering that has good insulation, can suppress cracks during heat resistance of the solder, and can follow the shape of the formed circuit. It is providing the soldering resist composition provided with property, and a printed wiring board using the same.
- a second object of the present invention is to provide a printed wiring board material that can realize a lower linear expansion coefficient than the conventional one and a printed wiring board using the same.
- a third object of the present invention is to provide a printed wiring board material that can suppress the occurrence of migration between holes and a printed wiring board using the printed wiring board material.
- a fourth object of the present invention is to provide a printed wiring board material capable of realizing a higher peel strength than the conventional one and a printed wiring board using the same.
- a fifth object of the present invention is to provide a printed wiring board material having excellent crack resistance and a printed wiring board using the printed wiring board material.
- the sixth object of the present invention is to use a printed wiring board material that has a high withstand voltage between circuits and can maintain high insulation reliability over a long period of time in a high-definition circuit or a large current application. It is to provide a printed wiring board.
- the present inventors have found that the first object of the present invention can be achieved by using a solder resist composition containing cellulose nanofibers having a predetermined fiber diameter, thereby completing the present invention. It came to.
- the solder resist composition of the present invention is characterized by containing a curable resin and cellulose nanofibers having a number average fiber diameter of 3 nm to 1000 nm.
- solder resist composition of the present invention a material selected from a thermosetting resin and a photocurable resin can be suitably used as the curable resin. Moreover, in the soldering resist composition of this invention, it is also preferable to use what contains carboxyl group-containing resin as said curable resin.
- the solder resist composition of the present invention preferably contains a layered silicate. Moreover, it is preferable that the soldering resist composition of this invention contains any one or both of a silicone compound and a fluorine compound. Furthermore, in the soldering resist composition of this invention, it is preferable that the number average fiber diameter of the said cellulose nanofiber is 3 nm or more and less than 1000 nm, and also contains a cellulose fiber with a number average fiber diameter of 1 micrometer or more.
- the cellulose nanofiber preferably has a carboxylate salt in its structure. Furthermore, in the solder resist composition of the present invention, it is preferable that the cellulose nanofiber is produced from lignocellulose.
- the dry film of the present invention is obtained by applying the solder resist composition of the present invention on a carrier film and drying it.
- the cured product of the present invention is a dried coating film obtained by applying the solder resist composition of the present invention on a substrate and drying, or the solder resist composition is applied on a carrier film and dried. It is obtained by curing a coating film obtained by laminating a dry film obtained by laminating on a base material.
- the printed wiring board of the present invention is characterized by having the cured product of the present invention.
- the present inventors have formulated a combination of cellulose nanofibers and layered silicates into a printed wiring board material, so that the linear expansion coefficient is smaller than when either one is blended. As a result, it was found that the second object of the present invention can be achieved, and the present invention has been completed.
- the printed wiring board material of the present invention is characterized by containing a binder component, cellulose nanofibers having a number average fiber diameter of 3 nm to 1000 nm, and layered silicate.
- thermoplastic resin and a curable resin can be suitably used as the binder component.
- the printed wiring board material of the present invention can be suitably used for solder resists, core materials, and interlayer insulating materials for multilayer printed wiring boards.
- the printed wiring board of the present invention is characterized by using the printed wiring board material of the present invention.
- the present inventors have found that the third object of the present invention can be achieved by using a printed wiring board material containing one or both of a silicone compound and a fluorine compound.
- the present invention has been completed.
- the printed wiring board material of the present invention includes a binder component, cellulose nanofibers having a number average fiber diameter of 3 nm to 1000 nm, and one or both of a silicone compound and a fluorine compound. Is.
- thermoplastic resin and a curable resin can be suitably used as the binder component.
- the printed wiring board material of the present invention can be suitably used for a core material and an interlayer insulating material of a multilayer printed wiring board.
- the printed wiring board of the present invention is characterized by using the printed wiring board material of the present invention.
- the present inventors can improve the peel strength by combining cellulose fibers having different fiber diameters with the printed wiring board material, and can achieve the fourth object of the present invention. As a result, the present invention has been completed.
- the printed wiring board material of the present invention includes a binder component, cellulose fibers having a number average fiber diameter of 1 ⁇ m or more, and cellulose nanofibers having a number average fiber diameter of 3 nm or more and less than 1000 nm. .
- thermoplastic resin and a curable resin can be suitably used as the binder component.
- the printed wiring board material of the present invention can be suitably used for a core material and an interlayer insulating material of a multilayer printed wiring board.
- the printed wiring board of the present invention is characterized by using the printed wiring board material of the present invention.
- the fifth object of the present invention can be achieved by using a material containing a specific cellulose nanofiber as a printed wiring board material, thereby completing the present invention. It came.
- the printed wiring board material of the present invention is characterized by including a binder component and cellulose nanofibers having a number average fiber diameter of 3 nm to 1000 nm having a carboxylate salt in the structure.
- the cellulose nanofiber was obtained by using natural cellulose fiber as a raw material and oxidizing the natural cellulose fiber in water using an N-oxyl compound as an oxidation catalyst and a co-oxidant. It is preferable.
- a thermoplastic resin and a curable resin can be suitably used as the binder component.
- the printed wiring board material of the present invention can be suitably used for a solder resist, a core material, and an interlayer insulating material of a multilayer printed wiring board.
- the printed wiring board of the present invention is characterized by using the printed wiring board material of the present invention.
- the present inventors have found that the sixth object of the present invention can be achieved by using a material containing a specific cellulose nanofiber as a printed wiring board material, thereby completing the present invention. It came.
- the printed wiring board material of the present invention is characterized by containing cellulose nanofibers produced from lignocellulose and having a number average fiber diameter of 3 nm to 1000 nm and a binder component.
- thermoplastic resin and a curable resin can be suitably used as the binder component.
- the printed wiring board material of the present invention can be suitably used for solder resists and core materials, and interlayer insulating materials for multilayer printed wiring boards.
- the printed wiring board of the present invention is characterized by using the printed wiring board material of the present invention.
- the present invention by including a curable resin and cellulose nanofibers having a number average fiber diameter of 3 nm to 1000 nm, it has good insulation and can suppress cracks during solder heat resistance. Further, it has become possible to realize a solder resist composition having a covering property capable of following the shape of the formed circuit and a printed wiring board using the same.
- a printed wiring board material capable of suppressing the occurrence of migration between holes by using one or both of a silicone compound and a fluorine compound, and the same are used.
- a printed wiring board can be realized.
- a printed wiring board material having excellent crack resistance and a printed wiring board using the same are realized by containing cellulose nanofibers having a carboxylate in the structure. It became possible.
- the withstand voltage between circuits is high in high-definition circuits and large current applications, and high over a long period of time.
- a printed wiring board material capable of maintaining insulation reliability and a printed wiring board using the same can be realized.
- the solder resist composition of the present invention is characterized in that it contains a curable resin and cellulose nanofibers having a number average fiber diameter of 3 nm to 1000 nm.
- Such cellulose nanofibers can be obtained as follows.
- cellulose nanofibers with a number average fiber diameter of 3 nm to 1000 nm As raw materials for cellulose nanofibers, use pulp made from natural plant fiber materials such as wood, hemp, bamboo, cotton, jute, kenaf, beet, agricultural waste, cloth, regenerated cellulose fibers such as rayon and cellophane, etc. Among them, pulp is particularly preferable.
- pulp chemical pulp such as kraft pulp and sulfite pulp, semi-chemical pulp, chemi-ground pulp, chemimechanical pulp, obtained by pulping plant raw materials chemically or mechanically, or a combination of both, Thermomechanical pulp, chemithermomechanical pulp, refiner mechanical pulp, groundwood pulp, deinked wastepaper pulp, magazine wastepaper pulp, corrugated wastepaper pulp and the like mainly composed of these plant fibers can be used.
- various kraft pulps derived from conifers having strong fiber strength for example, softwood unbleached kraft pulp, softwood oxygen bleached unbleached kraft pulp, and softwood bleached kraft pulp are particularly suitable.
- the raw material is mainly composed of cellulose, hemicellulose and lignin, and the content of lignin is usually about 0 to 40% by mass, particularly about 0 to 10% by mass.
- or a bleaching process can be performed as needed, and the amount of lignin can be adjusted.
- the lignin content can be measured by the Klason method.
- cellulose molecules are not a single molecule but regularly agglomerate to form crystalline microfibrils (cellulose nanofibers) that gather together and form the basic skeletal material of plants. ing. Therefore, in order to produce cellulose nanofibers from the above raw materials, a method of unraveling the fibers to the nano size by subjecting the raw materials to beating or crushing treatment, high-temperature high-pressure steam treatment, treatment with phosphate, etc. Can be used.
- the beating or pulverization treatment is a method of obtaining cellulose nanofibers by applying a force directly to the raw materials such as pulp, mechanically beating or pulverizing, and unraveling the fibers. More specifically, for example, pulp fibers or the like are mechanically treated with a high-pressure homogenizer or the like, and cellulose fibers that have been loosened to a fiber diameter of about 0.1 to 10 ⁇ m are made into an aqueous suspension of about 0.1 to 3% by mass. Furthermore, by repeatedly grinding or crushing this with a grinder or the like, cellulose nanofibers having a fiber diameter of about 10 to 100 nm can be obtained.
- the grinding or crushing treatment can be performed using, for example, a grinder “Pure Fine Mill” manufactured by Kurita Machine Seisakusho.
- This grinder is a stone mill that pulverizes raw materials into ultrafine particles by impact, centrifugal force and shearing force generated when the raw material passes through the gap between the upper and lower two grinders. Shearing, grinding, atomization Dispersion, emulsification and fibrillation can be performed simultaneously.
- the above grinding or crushing treatment can also be carried out using an ultrafine grinding machine “Supermass colloider” manufactured by Masuko Sangyo Co., Ltd.
- the Super Mass Collider is an attritor that enables ultra-fine atomization that feels like melting beyond the mere grinding area.
- the super mass collider is a stone mill type ultrafine grinding machine composed of two top and bottom non-porous grindstones whose spacing can be freely adjusted.
- the upper grindstone is fixed and the lower grindstone rotates at high speed.
- the raw material thrown into the hopper is fed into the gap between the upper and lower grinding stones by centrifugal force, and the raw material is gradually crushed by the strong compression, shearing, rolling frictional force, etc. generated there, and is made into ultrafine particles.
- the high temperature and high pressure steam treatment is a method of obtaining cellulose nanofibers by unraveling the fibers by exposing the raw materials such as pulp to high temperature and high pressure steam.
- the surface of the raw material such as the pulp is phosphorylated to weaken the bonding force between the cellulose fibers, and then the refiner treatment (grinding or crushing treatment) is performed.
- This is a treatment method for unraveling the fibers and obtaining cellulose nanofibers.
- the raw materials such as pulp are immersed in a solution containing 50% by mass of urea and 32% by mass of phosphoric acid, and the solution is sufficiently soaked between cellulose fibers at 60 ° C., and then heated at 180 ° C. After proceeding with phosphorylation and washing with water, it was hydrolyzed in a 3% by mass aqueous hydrochloric acid solution at 60 ° C.
- Cellulose nanofibers can be obtained by completing phosphorylation by treating at room temperature for about 20 minutes, and defibrating the treated product with a refiner (such as the above-mentioned grinder).
- the cellulose nanofiber used in the present invention may be chemically modified and / or physically modified to enhance functionality.
- a functional group is added by acetalization, acetylation, cyanoethylation, etherification, isocyanateation, etc., or inorganic substances such as silicate and titanate are combined by chemical reaction or sol-gel method, Or it can carry out by the method of coat
- the chemical modification method include a method in which cellulose nanofibers formed into a sheet are immersed in acetic anhydride and heated.
- PVD method physical vapor deposition
- CVD chemical vapor deposition
- electroless plating electrolytic plating
- electrolytic plating etc.
- PVD method physical vapor deposition
- the method of covering by the plating method etc. of this is mentioned. These modifications may be before the treatment or after the treatment.
- the number average fiber diameter of the cellulose nanofiber used in the present invention is required to be 3 nm to 1000 nm, preferably 3 nm to 200 nm, and more preferably 3 nm to 100 nm. Since the minimum diameter of the cellulose nanofiber single fiber is 3 nm, it is not possible to produce substantially less than 3 nm, and when it exceeds 1000 nm, it is necessary to add excessively in order to obtain the desired effect of the present invention. The film forming property is deteriorated.
- the number average fiber diameter of the cellulose nanofiber is observed with SEM (Scanning Electron Microscope; Scanning Electron Microscope), TEM (Transmission Electron Microscope; Transmission Electron Microscope), etc., and the diagonal line of the photograph is drawn. This is an average value obtained by extracting 12 points of fibers in the vicinity at random, removing the thickest fiber and the thinnest fiber, and measuring the remaining 10 points.
- the blending amount of the cellulose nanofiber used in the present invention is preferably 0.1 to 80% by mass, more preferably 0.2 to 70% by mass, based on the total amount of the composition excluding the solvent.
- the blending amount of the cellulose nanofiber is 0.1% by mass or more, the desired effect of the present invention can be obtained satisfactorily.
- film forming property improves.
- a method of forming a prepreg by forming the cellulose nanofibers into a sheet shape, impregnating the sheet-like cellulose nanofibers with a binder component and drying them can also be used.
- the content of the cellulose nanofiber in the prepreg is the same as the blending amount of the cellulose nanofiber.
- curable resin As a curable resin used for this invention, what is selected from a thermosetting resin and a photocurable resin is suitable, and these may be sufficient.
- thermosetting resin may be any resin that is cured by heating and exhibits electrical insulation, and examples thereof include epoxy compounds, oxetane compounds, melamine resins, and silicone resins.
- epoxy compounds oxetane compounds
- melamine resins melamine resins
- silicone resins silicone resins.
- an epoxy compound and / or an oxetane compound is preferably used.
- epoxy compound known and commonly used compounds having one or more epoxy groups can be used, and among them, compounds having two or more epoxy groups are preferable.
- monoepoxy compounds such as monoepoxy compounds such as butyl glycidyl ether, phenyl glycidyl ether, glycidyl (meth) acrylate, bisphenol A type epoxy resin, bisphenol S type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, Cresol novolac type epoxy resin, alicyclic epoxy resin, trimethylolpropane polyglycidyl ether, phenyl-1,3-diglycidyl ether, biphenyl-4,4′-diglycidyl ether, 1,6-hexanediol diglycidyl ether, Diglycidyl ether of ethylene glycol or propylene glycol, sorbitol polyglycidyl ether, tris (2,3-epoxypropyl) isocyanur
- epoxy compounds can be used alone or in combination of two or more according to the required properties.
- examples of the epoxy compound include Adekasizer O-130P, O-180A, D-32, D-55 manufactured by ADEKA Corporation, 604, 807, 828, 834, 1001, 1004, YL903 manufactured by Mitsubishi Chemical Corporation.
- Examples include, but are not limited to, 3000, NC-3100, TEPIC manufactured by Nissan Chemical Industries, Ltd., Bremer DGT, CP-50S, CP-50M manufactured by Nissan Oil Co., Ltd. These epoxy resins can be used alone or in combination of two or more.
- oxetane compound containing an oxetane ring represented by include 3-ethyl-3-hydroxymethyloxetane (Toago Synthetic Co., Ltd., trade name OXT-101), 3-ethyl-3- (phenoxymethyl) oxetane (Toagosei Co., Ltd., trade name OXT-211), 3-ethyl-3- (2-ethylhexyl) Siloxymethyl) oxetane (trade name OXT-212, manufactured by Toagosei Co., Ltd.), 1,4-bis ⁇ [(3-ethyl-3-oxetanyl) methoxy] methyl ⁇ benzene (trade name, manufactured by Toagosei Co., Ltd.) OXT-101, 3-ethyl-3- (phenoxymethyl) oxetane (Toagosei Co., Ltd., trade name OXT-211), 3-ethyl-3
- the photocurable resin may be any resin that is cured by irradiation with active energy rays and exhibits electrical insulation.
- the resin has one or more ethylenically unsaturated bonds.
- a compound is preferably used.
- photopolymerizable oligomers As the compound having an ethylenically unsaturated bond, known and commonly used photopolymerizable oligomers, photopolymerizable vinyl monomers, and the like are used.
- examples of the photopolymerizable oligomer include unsaturated polyester oligomers and (meth) acrylate oligomers.
- Examples of (meth) acrylate oligomers include phenol novolac epoxy (meth) acrylate, cresol novolac epoxy (meth) acrylate, epoxy (meth) acrylates such as bisphenol type epoxy (meth) acrylate, urethane (meth) acrylate, epoxy urethane (meta ) Acrylate, polyester (meth) acrylate, polyether (meth) acrylate, polybutadiene-modified (meth) acrylate, and the like.
- (meth) acrylate is a term which generically refers to acrylate, methacrylate and a mixture thereof, and the same applies to other similar expressions.
- photopolymerizable vinyl monomer known and commonly used monomers, for example, styrene derivatives such as styrene, chlorostyrene and ⁇ -methylstyrene; vinyl esters such as vinyl acetate, vinyl butyrate or vinyl benzoate; vinyl isobutyl ether, vinyl- vinyl ethers such as n-butyl ether, vinyl-t-butyl ether, vinyl-n-amyl ether, vinyl isoamyl ether, vinyl-n-octadecyl ether, vinyl cyclohexyl ether, ethylene glycol monobutyl vinyl ether, triethylene glycol monomethyl vinyl ether; acrylamide, Methacrylamide, N-hydroxymethylacrylamide, N-hydroxymethylmethacrylamide, N-methoxymethylacrylamide, N-ethoxymethylacrylamide (Meth) acrylamides such as rilamide and N-butoxymethylacrylamide; allyl compounds such as triallyl isocyan
- carboxyl group-containing resin Moreover, when making the soldering resist composition of this invention into the photosensitive resin composition of an alkali image development type, it is preferable to contain carboxyl group-containing resin.
- the carboxyl group-containing resin may be a carboxyl group-containing photosensitive resin having an ethylenically unsaturated group.
- the resins listed below (which may be either oligomers or polymers) can be preferably used.
- An unsaturated monocarboxylic acid is reacted with a copolymer of a compound having one epoxy group and an unsaturated double bond in each molecule and a compound having an unsaturated double bond, and formed by this reaction.
- a photosensitive carboxyl group-containing resin obtained by reacting a secondary hydroxyl group with a saturated or unsaturated polybasic acid anhydride.
- Photosensitive hydroxyl group and carboxyl group-containing resin obtained by reaction.
- a polyfunctional epoxy compound is reacted with a compound having one reactive group other than a hydroxyl group that reacts with two or more hydroxyl groups and an epoxy group in one molecule, and an unsaturated group-containing monocarboxylic acid.
- the carboxyl group-containing (meth) acrylic copolymer resin (2) which is the photosensitive carboxyl group-containing resin of (2), and (b) an oxirane ring and an ethylenically unsaturated group in one molecule.
- a copolymer resin having a carboxyl group obtained by a reaction with a compound having an aromatic group is preferred.
- a carboxyl group-containing (meth) acrylic copolymer resin is obtained by copolymerizing a (meth) acrylic acid ester and a compound having one unsaturated group and at least one carboxyl group in one molecule. can get.
- Examples of the (meth) acrylic acid ester constituting the copolymer resin (a) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl ( Hydroxyl groups such as (meth) acrylic acid alkyl esters such as (meth) acrylate, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, caprolactone-modified 2-hydroxyethyl (meth) acrylate, etc.
- (meth) acrylic acid esters methoxydiethylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, isooctyloxydiethylene glycol (meth) acrylate, phenoxy Triethylene glycol (meth) acrylate, methoxy triethylene glycol (meth) acrylate, glycol-modified (meth) acrylates such as methoxy polyethylene glycol (meth) acrylate. These may be used alone or in combination of two or more.
- examples of the compound having one unsaturated group and at least one carboxyl group in one molecule include acrylic acid, methacrylic acid, and a modified unsaturated monocarboxylic acid in which a chain is extended between the unsaturated group and the carboxylic acid.
- examples thereof include monocarboxylic acids, and those containing two or more carboxyl groups in the molecule, such as maleic acid. These may be used alone or in combination of two or more.
- Examples of the compound having an oxirane ring and an ethylenically unsaturated group in one molecule include glycidyl (meth) acrylate, ⁇ -methylglycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, Examples include 3,4-epoxycyclohexylethyl (meth) acrylate, 3,4-epoxycyclohexylbutyl (meth) acrylate, and 3,4-epoxycyclohexylmethylamino acrylate. Of these, 3,4-epoxycyclohexylmethyl (meth) acrylate is preferred.
- These (b) compounds having an oxirane ring and an ethylenically unsaturated group in one molecule may be used alone or in admixture of two or more.
- the carboxyl group-containing resin preferably has an acid value in the range of 50 to 200 mgKOH / g.
- the acid value is less than 50 mgKOH / g, it becomes difficult to remove the unexposed portion of the coating film of the solder resist composition with a weak alkaline aqueous solution.
- the acid value exceeds 200 mgKOH / g, problems such as inferior water resistance and electrical properties of the cured coating may occur.
- the mass average molecular weight of the carboxyl group-containing resin is preferably in the range of 5,000 to 100,000. When the mass average molecular weight is less than 5,000, the dryness to touch of the coating film of the solder resist composition tends to be inferior. On the other hand, when the mass average molecular weight exceeds 100,000, the developability and storage stability of the solder resist composition tend to deteriorate.
- Photopolymerization initiator When using a photocurable resin or a carboxyl group-containing photosensitive resin in the solder resist composition of the present invention, it is preferable to further add a photopolymerization initiator.
- the photopolymerization initiator include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzylmethyl ketal, and alkyl ethers thereof.
- tertiary amines such as triethanolamine and methyldiethanolamine; 2-dimethylaminoethylbenzoic acid, ethyl 4-dimethylaminobenzoate It can be used in combination with a photopolymerization initiation aid such as a benzoic acid derivative.
- the amount of the photopolymerization initiator used is usually a ratio that is usually used. For example, it is preferably 0.1 to 20 parts by weight, more preferably 100 parts by weight of the photocurable resin and / or carboxyl group-containing resin. Is 1 to 10 parts by mass.
- thermosetting resin in the soldering resist composition of this invention, a hardening
- curing agent and / or a hardening catalyst can be added further.
- the curing agent examples include polyfunctional phenol compounds, polycarboxylic acids and acid anhydrides thereof, aliphatic or aromatic primary or secondary amines, polyamide resins, and polymercapto compounds.
- polyfunctional phenol compounds, and polycarboxylic acids and acid anhydrides thereof are preferably used from the viewpoints of workability and insulation.
- any compound having two or more phenolic hydroxyl groups in one molecule may be used, and known ones can be used. Specific examples include phenol novolac resins, cresol novolac resins, bisphenol A, allylated bisphenol A, bisphenol F, bisphenol A novolac resins, vinyl phenol copolymer resins, and the like, which have high reactivity and increase heat resistance.
- a phenol novolac resin is particularly preferable because of its high effect.
- Such a polyfunctional phenol compound also undergoes an addition reaction with an epoxy compound and / or an oxetane compound in the presence of a suitable curing catalyst.
- the polycarboxylic acid and its acid anhydride are a compound having two or more carboxyl groups in one molecule and its acid anhydride, for example, a copolymer of (meth) acrylic acid, a copolymer of maleic anhydride And condensates of dibasic acids.
- Examples of commercially available products include John Kuryl (product group name) manufactured by BASF, SMA Resin (product group name) manufactured by Sartomer, and polyazeline acid anhydride manufactured by Shin Nippon Rika Co., Ltd.
- the amount of these curing agents to be blended is usually the proportion used, and is preferably 1 to 200 parts by mass, more preferably 10 to 100 parts by mass with respect to 100 parts by mass of the thermosetting resin.
- the curing catalyst is a compound that can be a curing catalyst in the reaction of the epoxy compound and / or oxetane compound and the like with the curing agent, or a compound that is a polymerization catalyst when no curing agent is used.
- the curing catalyst include a tertiary amine, a tertiary amine salt, a quaternary onium salt, a tertiary phosphine, a crown ether complex, and a phosphonium ylide.
- two or more types can be used in combination.
- imidazoles such as trade names 2E4MZ, C11Z, C17Z, and 2PZ
- AZINE compounds of imidazoles such as trade names 2MZ-A and 2E4MZ-A
- isocyanurates of imidazoles such as trade names 2MZ-OK and 2PZ-OK.
- Imidazole hydroxymethyl compounds such as trade names 2PHZ and 2P4MHZ (all trade names are manufactured by Shikoku Kasei Kogyo Co., Ltd.), dicyandiamide and derivatives thereof, melamine and derivatives thereof, diaminomaleonitrile and derivatives thereof, diethylenetriamine and triethylenetetramine , Tetraethylenepentamine, bis (hexamethylene) triamine, triethanolamine, diaminodiphenylmethane, organic acid dihydrazide, and other amines, 1,8-diazabicyclo [5,4,0] undecene-7 (trade name D U, manufactured by San Apro Co., Ltd.), 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5,5] undecane (trade name ATU, manufactured by Ajinomoto Co., Inc.), Alternatively, organic phosphine compounds such as triphenylphosphine, tricyclohexy
- the blending amount of these curing catalysts is sufficient at a normal ratio, and is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 3 parts by mass with respect to 100 parts by mass of the thermosetting resin. .
- the solder resist composition of the present invention preferably contains a layered silicate.
- a material with a significantly reduced linear expansion coefficient can be obtained with a smaller amount than when either one is combined due to a synergistic effect. It is.
- the following content can be used for the layered silicate.
- the solder resist composition of the present invention contains one or both of a silicone compound and a fluorine compound.
- the silicone compound and the fluorine compound can suppress the occurrence of migration between holes by combining with the cellulose nanofiber.
- the following content can be used for the silicone compound and the fluorine compound.
- the solder resist composition of the present invention preferably contains cellulose fibers having a number average fiber diameter of 1 ⁇ m or more and cellulose nanofibers having a number average fiber diameter of 3 nm or more and less than 1000 nm.
- a high peel strength can be realized by combining cellulose fibers having a number average fiber diameter of 1 ⁇ m or more and cellulose nanofibers having a number average fiber diameter of 3 nm or more and less than 1000 nm.
- the following content can be used for cellulose fibers having a number average fiber diameter of 1 ⁇ m or more.
- the cellulose nanofiber has a carboxylate in its structure.
- the crack resistance is improved.
- cellulose nanofibers having a carboxylate the following contents can be incorporated.
- the cellulose nanofiber is produced from lignocellulose.
- the cellulose nanofiber is manufactured from lignocellulose, in a high-definition circuit or a large current application, the withstand voltage between the circuits is high, and high insulation reliability can be maintained over a long period of time.
- lignocellulose nanofibers the following contents can be cited.
- thermosetting components include episulfide resins, amino resins such as melamine derivatives and benzoguanamine derivatives, polyisocyanate compounds, or block isocyanate compounds.
- a color index as a coloring pigment, dye, etc. can be used as a coloring agent.
- organic solvents examples include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, diethylene glycol Glycol ethers such as monoethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monoethyl ether; esters such as ethyl acetate, butyl acetate, cellosolve acetate, diethylene glycol monoethyl ether acetate and esterified products of the above glycol ethers; Alcohols such as ethanol, propanol, ethylene glycol, propylene glycol; Mention may be made of petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha,
- additives such as a defoaming and leveling agent, a thixotropy imparting agent / thickening agent, a coupling agent, a dispersant, and a flame retardant, may be included as necessary.
- Antifoaming and leveling agents include compounds such as silicone, modified silicone, mineral oil, vegetable oil, aliphatic alcohol, fatty acid, metal soap, fatty acid amide, polyoxyalkylene glycol, polyoxyalkylene alkyl ether, polyoxyalkylene fatty acid ester, etc. Etc. can be used.
- clay minerals such as kaolinite, smectite, montmorillonite, bentonite, talc, mica, zeolite, etc., silica gel, silica gel, amorphous inorganic particles, polyamide additives, modified urea additives, Wax-based additives can be used.
- alkoxy group is methoxy group, ethoxy group, acetyl, etc.
- reactive functional group is vinyl, methacryl, acrylic, epoxy, cyclic epoxy, mercapto, amino, diamino, acid anhydride, ureido, sulfide, Isocyanates and the like, for example, vinyl silane compounds such as vinyl ethoxylane, vinyl trimethoxysilane, vinyl tris ( ⁇ -methoxyethoxy) silane, ⁇ -methacryloxypropyltrimethoxylane, ⁇ -aminopropyltrimethoxylane, ⁇ - ⁇ - (aminoethyl) ⁇ -aminopropyltrimethoxysilane, N- ⁇ - (aminoethyl) ⁇ -aminopropylmethyldimethoxysilane, amino-based silane compounds such as ⁇ -ureidopropyltriethoxysilane, ⁇ -glycid
- Dispersants include polycarboxylic acid-based, naphthalene sulfonic acid formalin condensation-based, polyethylene glycol, polycarboxylic acid partial alkyl ester-based, polyether-based, polyalkylene polyamine-based polymeric dispersants, alkyl sulfonic acid-based, four Low molecular weight dispersants such as secondary ammonium series, higher alcohol alkylene oxide series, polyhydric alcohol ester series and alkylpolyamine series can be used.
- Flame retardants include hydrated metal such as aluminum hydroxide and magnesium hydroxide, red phosphorus, ammonium phosphate, ammonium carbonate, zinc borate, zinc stannate, molybdenum compound, bromine compound, chlorine compound, phosphate ester Phosphorus-containing polyol, phosphorus-containing amine, melamine cyanurate, melamine compound, triazine compound, guanidine compound, silicon polymer, and the like can be used.
- hydrated metal such as aluminum hydroxide and magnesium hydroxide, red phosphorus, ammonium phosphate, ammonium carbonate, zinc borate, zinc stannate, molybdenum compound, bromine compound, chlorine compound, phosphate ester Phosphorus-containing polyol, phosphorus-containing amine, melamine cyanurate, melamine compound, triazine compound, guanidine compound, silicon polymer, and the like can be used.
- ingredients include photoacid generators such as diazonium salts, sulfonium salts and iodonium salts, photobase generators such as carbamate compounds, ⁇ -aminoketone compounds and O-acyloxime compounds, hydroquinone, hydroquinone monomethyl ether, and t-butyl.
- Photoacid generators such as diazonium salts, sulfonium salts and iodonium salts
- photobase generators such as carbamate compounds, ⁇ -aminoketone compounds and O-acyloxime compounds
- hydroquinone hydroquinone monomethyl ether
- t-butyl polymerization inhibitors
- Polymerization inhibitors such as catechol, pyrogallol, phenothiazine
- inorganic fillers such as barium sulfate, spherical silica, hydrotalcite
- organic fillers such as silicon powder, nylon powder, fluorine powder, radical scavengers, ultraviolet absorb
- the solder resist composition of the present invention can be in the form of a dry film obtained by coating and drying on a carrier film (support).
- the solder resist composition of the present invention is diluted with the above organic solvent and adjusted to an appropriate viscosity, comma coater, blade coater, lip coater, rod coater, squeeze coater, reverse coater, transfer roll coater, It can be applied to a carrier film with a gravure coater, spray coater or the like to a uniform thickness, and is usually dried at a temperature of 50 to 130 ° C. for 1 to 30 minutes to form a dry coating film.
- the coating film thickness is not particularly limited, but in general, the film thickness after drying is suitably selected in the range of 10 to 150 ⁇ m, preferably 20 to 60 ⁇ m.
- a plastic film As the carrier film, a plastic film is used, and a plastic film such as a polyester film such as polyethylene terephthalate, a polyimide film, a polyamideimide film, a polypropylene film, or a polystyrene film is preferably used.
- the thickness of the carrier film is not particularly limited, but is generally appropriately selected within the range of 10 to 150 ⁇ m.
- a peelable cover film on the surface of the coating film for the purpose of preventing dust from adhering to the surface of the coating film after forming the coating film on the carrier film.
- a peelable cover film for example, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a surface-treated paper or the like can be used.
- the adhesive force between the coating film and the cover film is just to be smaller than the adhesive force of a coating film and a carrier film.
- a tack-free dry coating film is formed by applying the organic solvent contained in the composition at a temperature of about 60 to 100 ° C. by volatile drying (temporary drying). Can do.
- coated the said soldering resist composition on the carrier film and dried and wound up as a film this is a base material so that the coating film of a soldering resist composition may contact a base material with a laminator etc. After bonding together, the carrier film can be peeled off to form a coating layer on the substrate.
- These cured films can be photocured, for example, by irradiation with active energy rays, or heated to a temperature of 140 ° C. to 180 ° C. and thermally cured to obtain a cured product.
- the base material is paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth / non-woven cloth epoxy, glass cloth / paper epoxy, synthetic fiber.
- Volatile drying performed after the solder resist composition of the present invention is applied is performed using hot air in a dryer using an air heating type heat source such as a hot air circulation drying furnace, an IR furnace, a hot plate, or a convection oven. Can be carried out by using a method of bringing the gas into countercurrent contact, and a method of spraying the nozzle onto the support.
- an air heating type heat source such as a hot air circulation drying furnace, an IR furnace, a hot plate, or a convection oven.
- the exposure apparatus used for the active energy ray irradiation may be any apparatus that irradiates ultraviolet rays in the range of 350 to 450 nm, equipped with a high-pressure mercury lamp lamp, an ultra-high pressure mercury lamp lamp, a metal halide lamp, a mercury short arc lamp, etc.
- a direct drawing apparatus for example, a laser direct imaging apparatus that directly draws an image with a laser using CAD data from a computer
- the laser light source of the direct drawing machine either a gas laser or a solid laser may be used as long as it uses laser light having a maximum wavelength in the range of 350 to 410 nm. Exposure for image formation depends thickness, etc., but generally 20 ⁇ 800mJ / cm 2, preferably be in the range of 20 ⁇ 600mJ / cm 2.
- the developing method can be a dipping method, a shower method, a spray method, a brush method, etc.
- the developer is potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate.
- Alkaline aqueous solutions such as ammonia and amines can be used.
- the solder resist composition of the present invention has a good insulating property, an excellent crack resistance at the time of soldering heat resistance, and a good covering property capable of following the shape of the formed circuit. Therefore, a printed wiring board having excellent insulating properties and heat resistance can be obtained by using a cured product made of such a solder resist composition.
- the printed wiring board material of this embodiment may include a binder component, cellulose nanofibers having a number average fiber diameter of 3 nm to 1000 nm, and a layered silicate.
- the same cellulose nanofiber as in the first aspect can be used.
- the blending amount of the cellulose nanofibers in this embodiment is preferably 0.04 to 64% by mass, more preferably 0.08 to 56% by mass with respect to the total amount of the composition excluding the solvent.
- the blending amount of the cellulose nanofiber is 0.04% by mass or more, the effect of reducing the linear expansion coefficient can be favorably obtained.
- 64 mass% or less film forming property improves.
- the layered silicate is not particularly limited, but clay minerals and hydrotalcite compounds having swelling properties and / or cleavage properties, and similar compounds are preferable.
- these clay minerals include kaolinite, dickite, nacrite, halloysite, antigolite, chrysotile, pyrophyllite, montmorillonite, beidellite, nontronite, saponite, sauconite, stevensite, hectorite, tetrasilic mica, sodium.
- Examples include teniolite, muscovite, margarite, talc, vermiculite, phlogopite, xanthophyllite, chlorite.
- These layered silicates may be natural products or synthetic products. These layered silicates can be used alone or in combination.
- the shape of the layered silicate is not particularly limited, but it is difficult to cleave after layering when the layered silicate overlaps multiple layers.
- the thickness of the salt is preferably as thick as possible in one layer (about 1 nm). Further, those having an average length of 0.01 to 50 ⁇ m, preferably 0.05 to 10 ⁇ m, and an aspect ratio of 20 to 500, preferably 50 to 200 can be suitably used.
- the layered silicate has an inorganic cation capable of ion exchange between the layers.
- the ion-exchangeable inorganic cation is a metal ion such as sodium, potassium, or lithium existing on the surface of the layered silicate crystal. These ions have an ion exchange property with a cationic substance, and various substances having a cationic property can be inserted (intercalated) between the layers of the layered silicate by an ion exchange reaction.
- the cation exchange capacity (CEC) of the layered silicate is not particularly limited, but is preferably, for example, 25 to 200 meq / 100 g, more preferably 50 to 150 meq / 100 g, and 90 to 130 meq. More preferably, it is / 100g. If the cation exchange capacity of the layered silicate is 25 meq / 100 g or more, a sufficient amount of a cationic substance is inserted (intercalated) between the layers of the layered silicate by ion exchange, and the layers are sufficiently made organophilic. . On the other hand, if the cation exchange capacity is 200 meq / 100 g or less, the bonding strength between the layers of the layered silicate becomes too strong and the crystal flakes are not easily peeled off, and good dispersibility can be maintained.
- layered silicate satisfying the above preferred conditions include, for example, Sumecton SA manufactured by Kunimine Industry Co., Ltd., Kunipia F manufactured by Kunimine Industry Co., Ltd., Somasif ME-100 manufactured by Corp Chemical Co., Ltd. Examples of such products include Lucentite STN manufactured by Chemical Corporation.
- any general onium salt may be used as a layered silicate organic agent used in this embodiment. From the viewpoint of heat resistance, it is disclosed in JP-A-2004-107541. It is preferable to use an onium salt having a high thermal decomposition temperature.
- the method for containing the organophilic agent between the layered silicate layers is not particularly limited, but from the viewpoint that the synthesis operation is easy, the inorganic cation is made to be an organophilic agent by an ion exchange reaction. A method of containing them by exchanging them is preferable.
- the method for ion-exchanging the ion-exchangeable inorganic cation of the layered silicate with the organophilic agent is not particularly limited, and a known method can be used. Specifically, techniques such as ion exchange in water, ion exchange in alcohol, and ion exchange in a water / alcohol mixed solvent can be used.
- an organophilic agent is added and stirred to replace the inorganic cation between layers of the layered silicate with the organophilic agent. Thereafter, the unsubstituted organophilic agent is thoroughly washed, filtered and dried.
- the progress of the ion exchange can be confirmed by a known method. For example, the method of confirming the exchanged inorganic ions by ICP emission analysis of the filtrate, the method of confirming that the layer spacing of the layered silicate has been expanded by X-ray analysis, It can be confirmed that the inorganic cation of the layered silicate has been replaced with the organophilic agent by a method for confirming the presence of the organic agent.
- the ion exchange is preferably 0.05 equivalents (5% by mass) or more, more preferably 0.1 equivalents (10% by mass) or more with respect to 1 equivalent of inorganic ions capable of ion exchange of the layered silicate. Preferably, it is 0.5 equivalent (50 mass%) or more.
- Ion exchange is preferably performed at a temperature of 0 to 100 ° C., more preferably at a temperature range of 10 to 90 ° C., and even more preferably at a temperature range of 15 to 80 ° C.
- the amount of the layered silicate used in this embodiment is preferably 0.02 to 48% by mass, more preferably 0.04 to 42% by mass, based on the total amount of the composition excluding the solvent. is there.
- the compounding quantity of layered silicate is 0.02 mass% or more, the reduction effect of a linear expansion coefficient can be acquired favorably.
- film forming property improves.
- a material having a significantly reduced linear expansion coefficient with a smaller amount than when either one is blended due to a synergistic effect. can be obtained.
- the total amount of the cellulose nanofiber and the layered silicate in this embodiment is preferably 0.1 to 80% by mass, more preferably 0.2 to 70% by mass with respect to the total amount of the composition excluding the solvent. %.
- thermoplastic resins and curable resins such as thermosetting resins and photocurable resins can be suitably used.
- Thermoplastic resins include acrylic, modified acrylic, low density polyethylene, high density polyethylene, ethylene-vinyl acetate copolymer, polyethylene terephthalate, polypropylene, modified polypropylene, polystyrene, acrylonitrile-butadiene-styrene copolymer, acrylonitrile-styrene copolymer.
- General-purpose plastics such as polymers, cellulose acetate, polyvinyl alcohol, polyvinyl chloride, polyvinylidene chloride, polylactic acid, polyamide, thermoplastic polyurethane, polyacetal, polycarbonate, ultrahigh molecular weight polyethylene, polybutylene terephthalate, modified polyphenylene ether, polysulfone, Polyphenylene sulfide, polyethersulfone, polyetheretherketone, polyarylate, polyetherimide, poly Midimide, liquid crystal polymer, polyamide 6T, polyamide 9T, polytetrafluoroethylene, polyvinylidene fluoride, polyesterimide, engineering plastics such as thermoplastic polyimide, olefin, styrene, polyester, urethane, amide, vinyl chloride And thermoplastic elastomers such as hydrogenated systems.
- the thermosetting resin may be any resin that is cured by heating and exhibits electrical insulation.
- bisphenol A type epoxy resin bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol E type epoxy resin, bisphenol M type epoxy resin, bisphenol P type epoxy resin, bisphenol type epoxy resin such as bisphenol Z type epoxy resin, bisphenol A novolac type epoxy resin, phenol novolac type epoxy resin, novolac type epoxy resin such as cresol novolac epoxy resin, biphenyl type epoxy Resin, biphenyl aralkyl type epoxy resin, aryl alkylene type epoxy resin, tetraphenylol ethane type epoxy resin, naphthalene type epoxy resin, anthracene type epoxy resin Resin, phenoxy type epoxy resin, dicyclopentadiene type epoxy resin, norbornene type epoxy resin, adamantane type epoxy resin, fluorene type epoxy resin, glycidyl methacrylate copolymer epoxy resin, copolymer epoxy resin of cyclo
- Phenol resin such as resol type phenol resin such as modified oil-modified resol phenol resin, phenoxy resin, urea (urea) resin, triazine ring-containing resin such as melamine resin, unsaturated polyester resin, bismaleimide resin, diallyl phthalate resin, silicone Resin, resin having benzoxazine ring, norbornene resin, cyanate resin, isocyanate resin, urethane resin, benzocyclobutene resin, maleimide resin, bismaleimide triazine resin, A polyazomethine resin, a thermosetting polyimide, etc. are mentioned.
- resol type phenol resin such as modified oil-modified resol phenol resin, phenoxy resin, urea (urea) resin, triazine ring-containing resin such as melamine resin, unsaturated polyester resin, bismaleimide resin, diallyl phthalate resin, silicone Resin, resin having benzoxazine ring, norbornene resin
- the radically polymerizable photocurable resin may be any resin that is cured by irradiation with active energy rays and exhibits electrical insulation, and in particular, a compound having one or more ethylenically unsaturated bonds in the molecule is preferably used. It is done.
- a compound having one or more ethylenically unsaturated bonds known and commonly used photopolymerizable oligomers and photopolymerizable vinyl monomers are used.
- Examples of the photopolymerizable oligomer include unsaturated polyester oligomers and (meth) acrylate oligomers.
- Examples of (meth) acrylate oligomers include phenol novolac epoxy (meth) acrylate, cresol novolac epoxy (meth) acrylate, epoxy (meth) acrylates such as bisphenol type epoxy (meth) acrylate, urethane (meth) acrylate, epoxy urethane (meta ) Acrylate, polyester (meth) acrylate, polyether (meth) acrylate, polybutadiene-modified (meth) acrylate, and the like.
- (meth) acrylate is a term which generically refers to acrylate, methacrylate and a mixture thereof, and the same applies to other similar expressions.
- photopolymerizable vinyl monomer known and commonly used monomers, for example, styrene derivatives such as styrene, chlorostyrene and ⁇ -methylstyrene; vinyl esters such as vinyl acetate, vinyl butyrate or vinyl benzoate; vinyl isobutyl ether, vinyl- vinyl ethers such as n-butyl ether, vinyl-t-butyl ether, vinyl-n-amyl ether, vinyl isoamyl ether, vinyl-n-octadecyl ether, vinyl cyclohexyl ether, ethylene glycol monobutyl vinyl ether, triethylene glycol monomethyl vinyl ether; acrylamide, Methacrylamide, N-hydroxymethylacrylamide, N-hydroxymethylmethacrylamide, N-methoxymethylacrylamide, N-ethoxymethylacrylamide (Meth) acrylamides such as rilamide and N-butoxymethylacrylamide; allyl compounds such as triallyl isocyan
- an alicyclic epoxy compound As the cationic polymerizable photocurable resin, an alicyclic epoxy compound, an oxetane compound, a vinyl ether compound, or the like can be suitably used.
- alicyclic epoxy compounds include 3,4,3 ′, 4′-diepoxybicyclohexyl, 2,2-bis (3,4-epoxycyclohexyl) propane, and 2,2-bis (3,4-epoxy).
- oxetane compound examples include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [(3-ethyl-3-oxetanylmethoxy) methyl] ether, 1,4-bis [(3-methyl-3- Oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, (3-methyl-3-oxetanyl) methyl acrylate, (3-ethyl-3-oxetanyl) methyl acrylate
- polyfunctional oxetanes such as (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate and oligomers or copolymers thereof, oxetane alcohol and novolak resin, poly (p -Hydroxystyrene
- vinyl ether compounds include cyclic ether type vinyl ethers such as isosorbite divinyl ether and oxanorbornene divinyl ether (vinyl ethers having a cyclic ether group such as oxirane ring, oxetane ring and oxolane ring); aryl vinyl ethers such as phenyl vinyl ether; n-butyl vinyl ether Alkyl vinyl ethers such as octyl vinyl ether; cycloalkyl vinyl ethers such as cyclohexyl vinyl ether; polyfunctional vinyl ethers such as hydroquinone divinyl ether, 1,4-butanediol divinyl ether, cyclohexane divinyl ether, cyclohexanedimethanol divinyl ether, ⁇ and / or ⁇ position And vinyl ether compounds having a substituent such as an alkyl group and an allyl group.
- HEVE 2-hydroxyethyl vinyl ether
- DEGV diethylene glycol monovinyl ether
- HBVE 2-hydroxybutyl vinyl ether
- triethylene glycol divinyl ether manufactured by Maruzen Petrochemical Co., Ltd.
- the printed wiring board material of this embodiment is used as an alkali development type photo solder resist that can be developed with an alkaline aqueous solution, it is also preferable to use a carboxyl group-containing resin as a binder component.
- Carboxyl group-containing resin As the carboxyl group-containing resin, any of a photosensitive carboxyl group-containing resin having at least one photosensitive unsaturated double bond and a carboxyl group-containing resin having no photosensitive unsaturated double bond can be used. However, it is not limited to a specific one. As the carboxyl group-containing resin, the resins mentioned in the first embodiment can be suitably used.
- Examples of other commonly used ingredients include a curing catalyst, a photopolymerization initiator, a colorant, and an organic solvent.
- the curing catalyst is mainly for curing a thermosetting resin among curable resins.
- imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2- Imidazole derivatives such as phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole; dicyandiamide, benzyldimethylamine, 4- (dimethylamino) Amine compounds such as —N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl-N, N-dimethylbenzylamine; hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide; Phosphorus such as phenylphosphine Such compounds, and the like.
- Examples of commercially available products include 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (manufactured by Shikoku Kasei Kogyo Co., Ltd.), U-CAT3503N, U-CAT3502T, DBU, DBN, U-CATSA102, U- CAT5002 (manufactured by San Apro Co., Ltd.) and the like may be mentioned, and these may be used alone or in admixture of two or more.
- the photopolymerization initiator is for curing the photocurable resin among the curable resins, for example, benzoin and benzoin alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether.
- Acetophenones such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone; 2-methyl -1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2- (dimethylamino) ) -2-[(4-Methylphenyl) methyl Aminoalkylphenones such as 1- [4- (4-morpholinyl) phenyl] -1-butanone; anthraquinones such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-tertiarybutylanthraquinone, 1-chloroanthraquinone Thioxanthones such
- These photopolymerization initiators can be used alone or in combination of two or more.
- the colorant a known and conventional one represented by a color index as a color pigment, dye, or the like as mentioned in the first embodiment can be used.
- organic solvent those mentioned in the first aspect can be used.
- additives such as a defoaming and leveling agent, a thixotropy imparting agent / thickening agent, a coupling agent, a dispersant, and a flame retardant, may be included as necessary.
- a defoaming and leveling agent such as a thixotropy imparting agent / thickening agent, a coupling agent, a dispersant, and a flame retardant
- the defoaming agent / leveling agent such as a defoaming and leveling agent, a thixotropy imparting agent / thickening agent, a coupling agent, a dispersant, and a flame retardant.
- fine particle silica, silica gel, amorphous inorganic particles, polyamide-based additive, modified urea-based additive, wax-based additive and the like can be used.
- ingredients include photoacid generators such as diazonium salts, sulfonium salts and iodonium salts, photobase generators such as carbamate compounds, ⁇ -aminoketone compounds and O-acyloxime compounds, and inorganic fillers such as barium sulfate and spherical silica.
- organic fillers such as silicon powder, nylon powder and fluorine powder, radical scavengers, ultraviolet absorbers, peroxide decomposers, thermal polymerization inhibitors, adhesion promoters, rust inhibitors and the like.
- the printed wiring board material according to this aspect of the configuration as described above can be suitably applied to the solder resist and the core material, and can be suitably used for the interlayer insulating material of the multilayer printed wiring board, Thereby, in the obtained printed wiring board, the expected effect of this aspect can be acquired. Further, when the present embodiment is applied to a printed wiring board material, for example, a method of forming the cellulose nanofibers into a sheet shape, impregnating the sheet-like cellulose nanofibers with a binder component, and drying to prepare a prepreg. Can be used.
- FIG. 1 is a partial cross-sectional view showing a configuration example of a multilayer printed wiring board according to this embodiment.
- the illustrated multilayer printed wiring board can be manufactured, for example, as follows. First, a through hole is formed in the core substrate 2 on which the conductor pattern 1 is formed. The through hole can be formed by an appropriate means such as a drill, a die punch, or laser light. Then, a roughening process is performed using a roughening agent. Generally, the roughening treatment is carried out by swelling with an organic solvent such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, or methoxypropanol, or an alkaline aqueous solution such as caustic soda or caustic potash. It is carried out using an oxidizing agent such as salt, ozone, hydrogen peroxide / sulfuric acid or nitric acid.
- an organic solvent such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, or methoxy
- the conductor pattern 3 is formed by a combination of electroless plating or electrolytic plating.
- the step of forming the conductor layer by electroless plating is a step of immersing in an aqueous solution containing a plating catalyst, adsorbing the catalyst, and then immersing in a plating solution to deposit the plating.
- a predetermined circuit pattern is formed on the conductor layer on the surface of the core substrate 2 in accordance with a conventional method (subtractive method, semi-additive method, etc.), and a conductor pattern 3 is formed on both sides as shown.
- a plated layer is also formed in the through hole, and as a result, the connection portion 4 of the conductor pattern 3 of the multilayer printed wiring board and the connection portion 1a of the conductor pattern 1 are electrically connected.
- Through hole 5 is formed.
- the interlayer insulating layer 6 is formed by heating and curing.
- the interlayer insulating layer 6 is formed by laminating or hot plate pressing and heat curing.
- vias 7 for electrically connecting the connection portions of the conductor layers are formed by appropriate means such as laser light, and the conductor pattern 8 is formed by the same method as the conductor pattern 3.
- the interlayer insulating layer 9, the via 10 and the conductor pattern 11 are formed by the same method.
- a multilayer printed wiring board is manufactured by forming the solder resist layer 12 in the outermost layer.
- a single-sided substrate or a double-sided substrate may be used instead of the multilayer substrate.
- the printed wiring board material of this embodiment may contain a binder component, cellulose nanofibers having a number average fiber diameter of 3 nm to 1000 nm, and one or both of a silicone compound and a fluorine compound.
- the same cellulose nanofiber as in the first aspect can be used.
- the number average fiber diameter of the cellulose nanofibers in this embodiment is required to be 3 nm to 1000 nm, preferably 3 nm to 200 nm, more preferably 3 nm to 100 nm. Since the minimum diameter of the cellulose nanofiber single fiber is 3 nm, it cannot be produced substantially less than 3 nm, and when it exceeds 1000 nm, the dispersibility with the binder component is deteriorated. In addition, the number average fiber diameter of the cellulose nanofiber is observed with SEM (Scanning Electron Microscope; Scanning Electron Microscope), TEM (Transmission Electron Microscope; Transmission Electron Microscope), etc., and the diagonal line of the photograph is drawn. This is an average value obtained by extracting 12 points of fibers in the vicinity at random, removing the thickest fiber and the thinnest fiber, and measuring the remaining 10 points.
- the blending amount of the cellulose nanofibers in this embodiment is preferably 0.1 to 80% by mass, more preferably 0.2 to 70% by mass with respect to the total amount of the composition excluding the solvent.
- the blending amount of the cellulose nanofiber is 0.1% by mass or more, the desired effect of this aspect can be obtained satisfactorily.
- film forming property improves.
- silicone compound examples include polydimethylsiloxane, polyalkylphenylsiloxane, alkyl-modified silicone oil, polyether-modified silicone oil, polyalkylsiloxane, polymethylsilsesquioxane, polyalkylhydrogensiloxane, polyalkylalkenylsiloxane, and polymethylphenyl.
- silicone compound examples include siloxane, aralkyl-modified silicone oil, and alkylaralkyl-modified silicone oil.
- fluorine compound examples include fluorine-based resins having a perfluoroalkyl group or a perfluoroalkenyl group in the molecule.
- Commercially available products include, for example, MegaFuck F-444, F-472, F-477, F-552, F-553, F-554, F-443, F-470, F- 470, F-475, F-482, F-482, F-487, F-487, R-30, RS-75 (manufactured by DIC Corporation), F-top EF301, 303, 352 (Shin-Akita Kasei Co., Ltd.), Florad FC-430, FC-431 (Sumitomo 3M Co., Ltd.), Asahi Guard AG-E300D, Surflon S-382, SC-101, SC- 102, SC-103, SC-104, SC-105, SC-106 (above, Asahi Glass Co., Ltd.), BM-1000, BM
- the amount of one or both of the silicone compound and fluorine compound used in this embodiment is preferably 0.01 to 20 parts by mass, more preferably 0.01 to 100 parts by mass of the binder component. To 10 parts by mass, more preferably 0.05 to 3 parts by mass.
- the blending amount of either one or both of the silicone compound and the fluorine compound is 0.01% by mass or more, the desired effect of this embodiment can be obtained satisfactorily.
- film forming property improves.
- Binder component As the binder component used in this embodiment, the same components as in the second embodiment can be used.
- Carboxyl group-containing resin Moreover, when using the printed wiring board material of this aspect as an alkali development type photo solder resist which can be developed with an alkaline aqueous solution, it is also preferable to use a carboxyl group-containing resin as a binder component. As the carboxyl group-containing resin, the same resin as in the second embodiment can be used.
- cellulose nanofibers In the printed wiring board material of this embodiment, cellulose nanofibers, a binder component, and any one or both of a silicone compound and a fluorine compound, and other conventional compounding components are appropriately blended depending on the application. Is possible.
- Examples of other conventional compounding components include a curing catalyst, a photopolymerization initiator, a colorant, and an organic solvent.
- a curing catalyst a photopolymerization initiator, a colorant, and an organic solvent.
- photopolymerization initiator, colorant and organic solvent those mentioned in the second embodiment can be used.
- additives such as a defoaming and leveling agent, a thixotropy imparting agent / thickening agent, a coupling agent, a dispersant, and a flame retardant, may be included as necessary.
- a defoaming and leveling agent such as mineral oil, vegetable oil, aliphatic alcohol, fatty acid, metal soap, fatty acid amide, polyoxyalkylene glycol, polyoxyalkylene alkyl ether, polyoxyalkylene fatty acid ester, and the like can be used.
- the thixotropy imparting agent / thickening agent, coupling agent, dispersant, and flame retardant those described in the first aspect can be used.
- ingredients include photoacid generators such as diazonium salts, sulfonium salts, iodonium salts, photobase generators such as carbamate compounds, ⁇ -aminoketone compounds, O-acyloxime compounds, barium sulfate, spherical silica, hydrotalcite.
- photoacid generators such as diazonium salts, sulfonium salts, iodonium salts
- photobase generators such as carbamate compounds, ⁇ -aminoketone compounds, O-acyloxime compounds, barium sulfate, spherical silica, hydrotalcite.
- inorganic fillers such as silicon powder, nylon powder and fluorine powder, radical scavengers, ultraviolet absorbers, peroxide decomposers, thermal polymerization inhibitors, adhesion promoters, rust inhibitors and the like.
- the printed wiring board material according to this aspect of the configuration as described above can be suitably applied to the core material, and can also be suitably used for the interlayer insulating material of the multilayer printed wiring board.
- the desired effect of this aspect can be obtained.
- the present embodiment is applied to a printed wiring board material, for example, the cellulose nanofiber is formed into a sheet, and the sheet-like cellulose nanofiber is bonded to any one of a binder component, a silicone compound, and a fluorine compound.
- a method of preparing a prepreg by impregnating and drying a composition comprising one or both of them can also be used.
- the multilayer printed wiring board according to this embodiment as shown in FIG. 1 can be manufactured in the same manner as in the second embodiment.
- the printed wiring board material of this embodiment may include a binder component, cellulose fibers having a number average fiber diameter of 1 ⁇ m or more, and cellulose nanofibers having a number average fiber diameter of 3 nm or more and less than 1000 nm.
- the cellulose fiber and cellulose nanofiber can be obtained as follows.
- Examples of the raw material for cellulose fiber and cellulose nanofiber include the same materials as in the first embodiment.
- pulp is mechanically treated with a high-pressure homogenizer or the like to loosen the fiber to a fiber diameter of about 1 to 10 ⁇ m, and the cellulose fiber is made into a water suspension of about 0.1 to 3% by mass. Obtainable.
- the above raw materials are subjected to grinding or crushing treatment after beating or pulverizing treatment, high-temperature and high-pressure steam treatment, treatment with phosphate, etc.
- the raw material can be unraveled to nano size.
- cellulose nanofibers having a fiber diameter of about 10 to 100 nm can be obtained by repeatedly unraveling the cellulose fibers obtained by beating or crushing treatment with a grinder or the like.
- the above grinding or crushing treatment, the above high temperature and high pressure steam treatment, and the above treatment with phosphate and the like can be carried out in the same manner as in the first embodiment.
- cellulose fiber and cellulose nanofiber used in this embodiment may be chemically modified and / or physically modified to enhance functionality, as in the first embodiment.
- the number average fiber diameters of the cellulose fibers and cellulose nanofibers used in this embodiment are values obtained in the same manner as in the first embodiment.
- the number average fiber diameter of the cellulose nanofibers used in this embodiment needs to be 3 nm or more and less than 1000 nm, preferably 3 nm to 200 nm, more preferably 3 nm to 100 nm. Since the minimum diameter of the cellulose nanofiber monofilament is 3 nm, it cannot be produced substantially less than 3 nm, and if it is 1000 nm or more, the desired effect cannot be obtained.
- the number average fiber diameter of the cellulose fibers needs to be 1 ⁇ m or more, preferably 1 ⁇ m to 50 ⁇ m, more preferably 1 ⁇ m to 20 ⁇ m. If the number average fiber diameter of the cellulose fiber is smaller than the above range, the desired effect cannot be obtained.
- the treatment is stopped in the middle so that the whole amount is not unraveled, leaving the cellulose fibers in the range of the number average fiber diameter.
- a mixture of cellulose fiber and cellulose nanofiber that satisfies the conditions of this embodiment can be obtained. Therefore, in the printed wiring board material of this embodiment, in addition to the cellulose fiber and the cellulose nanofiber satisfying the range of the specific number average fiber diameter, the number average fiber diameter is outside the range of the specific number average fiber diameter.
- Cellulose fibers may be included.
- cellulose fiber a commercially available product can be appropriately used as long as it satisfies the condition of the number average fiber diameter, and is not particularly limited.
- the mass ratio of the cellulose fiber to the cellulose nanofiber in this embodiment is preferably 9: 1 to 1: 9, more preferably 8: 2 to 2: 8. By setting it within this range, higher peel strength can be obtained.
- the total amount of the cellulose fiber and the cellulose nanofiber in this embodiment is preferably 0.5 to 80% by mass, more preferably 1 to 70% by mass with respect to the total amount of the composition excluding the solvent. is there.
- the total amount of the cellulose fibers and the cellulose nanofibers 0.5% by mass or more, higher peel strength can be obtained, and by 80% by mass or less, good film-forming properties are obtained. Can be obtained.
- Binder component As the binder component used in this embodiment, the same components as in the second embodiment can be used.
- Carboxyl group-containing resin Moreover, when using the printed wiring board material of this aspect as an alkali development type insulating material that can be developed with an alkaline aqueous solution, it is also preferable to use a carboxyl group-containing resin as a binder component. As the carboxyl group-containing resin, the same resin as in the second embodiment can be used.
- the printed wiring board material of the present embodiment includes cellulose fiber, cellulose nanofiber and binder component, and other conventional compounding components, for example, a curing catalyst, a photopolymerization initiator, a colorant, an organic solvent, depending on the application. It is possible to mix
- a curing catalyst, photopolymerization initiator, colorant and organic solvent those mentioned in the second embodiment can be used.
- additives such as a defoaming and leveling agent, a thixotropy imparting agent / thickening agent, a coupling agent, a dispersant, and a flame retardant, may be included as necessary.
- a defoaming and leveling agent such as a defoaming and leveling agent, a thixotropy imparting agent / thickening agent, a coupling agent, a dispersant, and a flame retardant
- the antifoaming agent / leveling agent, thixotropy imparting agent / thickening agent, coupling agent, dispersant, and flame retardant those mentioned in the first embodiment can be used.
- ingredients include photoacid generators such as diazonium salts, sulfonium salts, iodonium salts, photobase generators such as carbamate compounds, ⁇ -aminoketone compounds, O-acyloxime compounds, barium sulfate, spherical silica, hydrotalcite.
- photoacid generators such as diazonium salts, sulfonium salts, iodonium salts
- photobase generators such as carbamate compounds, ⁇ -aminoketone compounds, O-acyloxime compounds, barium sulfate, spherical silica, hydrotalcite.
- inorganic fillers such as silicon powder, nylon powder and fluorine powder, radical scavengers, ultraviolet absorbers, peroxide decomposers, thermal polymerization inhibitors, adhesion promoters, rust inhibitors and the like.
- the printed wiring board material according to this aspect having the configuration as described above can be suitably used for an interlayer insulating material of a core material and a multilayer printed wiring board.
- the desired effect of the embodiment can be obtained.
- a method of forming a prepreg by forming a mixture of the cellulose fiber and cellulose nanofiber into a sheet, impregnating the sheet with a binder component, and drying the mixture. can be used.
- the multilayer printed wiring board according to this embodiment as shown in FIG. 1 can be manufactured in the same manner as in the second embodiment.
- the printed wiring board material of this embodiment may include a binder component and cellulose nanofibers having a number average fiber diameter of 3 nm to 1000 nm having a carboxylate salt in the structure.
- cellulose nanofibers can be obtained by oxidizing natural cellulose fibers and then refining them according to the following.
- an aqueous dispersion is prepared by dispersing natural cellulose fibers in about 10 to 1000 times (mass basis) of water on an absolute dry basis using a mixer or the like.
- the natural cellulose fiber used as a raw material for the cellulose nanofiber include wood pulp such as softwood pulp and hardwood pulp, non-wood pulp such as straw pulp and bagasse pulp, cotton pulp such as cotton lint and cotton linter, Examples include bacterial cellulose. These may be used individually by 1 type, or may be used in combination of 2 or more types as appropriate. Further, these natural cellulose fibers may be subjected to a treatment such as beating in order to increase the surface area in advance.
- N-oxyl compounds include TEMPO (2,2,6,6-tetramethylpiperidine-N-oxyl), 4-carboxy-TEMPO, 4-acetamido-TEMPO, 4-amino-TEMPO, 4 -Dimethylamino-TEMPO, 4-phosphonooxy-TEMPO, 4-hydroxy TEMPO, 4-oxy TEMPO, 4-methoxy TEMPO, 4- (2-bromoacetamido) -TEMPO, 2-azaadamantane N-oxyl, etc.
- TEMPO derivatives having various functional groups at the C4 position can be used.
- a catalytic amount is sufficient, and it can usually be in a range of 0.1 to 10% by mass with respect to natural cellulose fiber on an absolute dry basis.
- an oxidizing agent and a co-oxidizing agent are used in combination.
- the oxidizing agent include halous acid, hypohalous acid and perhalogenic acid and salts thereof, hydrogen peroxide, perorganic acid, among which sodium hypochlorite and sodium hypobromite.
- Alkali metal hypohalites such as are preferred.
- an alkali metal bromide such as sodium bromide can be used as the co-oxidant.
- the amount of the oxidizing agent used is usually in the range of about 1 to 100% by mass based on the absolute dry standard relative to the natural cellulose fiber, and the amount of the co-oxidant used is usually based on the absolute dry standard relative to the natural cellulose fiber Is about 1 to 30% by mass.
- the pH of the aqueous dispersion in the range of 9 to 12 from the viewpoint of efficiently proceeding the oxidation reaction.
- the temperature of the aqueous dispersion during the oxidation treatment can be arbitrarily set in the range of 1 to 50 ° C., and the reaction can be performed at room temperature without temperature control.
- the reaction time can be in the range of 1 to 240 minutes.
- a penetrant can be added to the aqueous dispersion in order to allow the drug to penetrate into the inside of the natural cellulose fiber and introduce more carboxyl groups into the fiber surface.
- penetrating agent examples include anionic surfactants such as carboxylate, sulfate ester salt, sulfonate salt, and phosphate ester salt, and nonionic surfactants such as polyethylene glycol type and polyhydric alcohol type. .
- the oxidation treatment of the natural cellulose fiber it is preferable to carry out a purification treatment to remove impurities such as unreacted oxidant and various by-products contained in the aqueous dispersion prior to refinement.
- a technique of repeatedly washing and filtering the oxidized natural cellulose fiber can be used.
- the natural cellulose fiber obtained after the refining treatment is usually subjected to a refining treatment in a state impregnated with an appropriate amount of water. However, if necessary, the natural cellulose fiber may be dried to obtain a fibrous or powdery form.
- the solvent as a dispersion medium used in the micronization treatment is usually preferably water, but if desired, alcohols (methanol, ethanol, isopropanol, isobutanol, sec-butanol, tert-butanol, methyl cellosolve, ethyl cellosolve, Ethylene glycol, glycerin, etc.), ethers (ethylene glycol dimethyl ether, 1,4-dioxane, tetrahydrofuran, etc.), ketones (acetone, methyl ethyl ketone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, etc.), etc.
- alcohols methanol, ethanol, isopropanol, isobutanol, sec-butanol, tert-butanol, methyl cellosolve, ethyl cellosolve, Ethylene glycol, glycerin
- a water-soluble organic solvent may be used, or a mixture thereof may be used.
- the solid content concentration of the natural cellulose fiber in the dispersion of these solvents is preferably 50% by mass or less. When the solid content concentration of the natural cellulose fiber exceeds 50% by mass, extremely high energy is required for dispersion, which is not preferable.
- Refinement of natural cellulose treatment includes low-pressure homogenizers, high-pressure homogenizers, grinders, cutter mills, ball mills, jet mills, beating machines, disintegrators, short-screw extruders, twin-screw extruders, ultrasonic agitators, household juicer mixers, etc. This can be done using a dispersing device.
- the cellulose nanofibers obtained by the refinement treatment can be made into a suspension in which the solid content concentration is adjusted, or a dried powder, as desired.
- a suspension only water may be used as a dispersion medium, and water and other organic solvents, for example, alcohols such as ethanol, surfactants, acids, bases, etc.
- a mixed solvent may be used.
- the hydroxyl group at the C6 position of the structural unit of the cellulose molecule is selectively oxidized to a carboxyl group via an aldehyde group, and the content of the carboxyl group is 0.1.
- This highly crystalline cellulose nanofiber has a cellulose I-type crystal structure. This means that the cellulose nanofibers are those obtained by surface-oxidizing naturally-derived cellulose molecules having an I-type crystal structure.
- natural cellulose fibers have a high-order solid structure formed by a bundle of fine fibers called microfibrils produced in the process of biosynthesis, and a strong cohesive force between the microfibrils (between surfaces).
- the cellulose nanofibers can be obtained by weakening the hydrogen bond) by introducing an aldehyde group or a carboxyl group by an oxidation treatment, and further through a refinement treatment. By adjusting the conditions of the oxidation treatment, the content of the carboxyl group is increased or decreased, the polarity is changed, or by the electrostatic repulsion or refinement treatment of the carboxyl group, the average fiber diameter or average fiber length of the cellulose nanofiber, The average aspect ratio can be controlled.
- the introduction of a carboxyl group into the cellulose molecule of the cellulose nanofibers indicates that in a sample from which moisture has been completely removed, absorption due to a carbonyl group (1608 cm ⁇ 1 ) in the total reflection infrared spectroscopic spectrum (ATR). This can be confirmed by the presence of the vicinity. In the case of a carboxyl group (COOH), there is an absorption at 1730 cm ⁇ 1 in the above measurement.
- dehalogenation treatment can be performed for the purpose of removing such residual halogen atoms.
- the dehalogenation treatment can be performed by immersing the oxidized natural cellulose fiber in a hydrogen peroxide solution or an ozone solution.
- the oxidized natural cellulose fiber is added to a hydrogen peroxide solution having a concentration of 0.1 to 100 g / L in a bath ratio of about 1: 5 to 1: 100, preferably 1:10 to 1. : Immerse under conditions of about 60 (mass ratio).
- the concentration of the hydrogen peroxide solution is preferably 1 to 50 g / L, and more preferably 5 to 20 g / L.
- the pH of the hydrogen peroxide solution is preferably 8 to 11, more preferably 9.5 to 10.7.
- the number average fiber diameter of the cellulose nanofiber used in this embodiment needs to be 3 nm to 1000 nm, preferably 3 nm to 200 nm, and more preferably 3 nm to 100 nm. Since the minimum diameter of cellulose nanofiber single fiber is 3 nm, less than 3 nm cannot be manufactured substantially, and when the number average fiber diameter exceeds 1000 nm, it is excessive to obtain the desired effect of this embodiment. It is necessary to add, and film forming property deteriorates. In addition, the number average fiber diameter of the cellulose nanofiber is observed with SEM (Scanning Electron Microscope; Scanning Electron Microscope), TEM (Transmission Electron Microscope; Transmission Electron Microscope), etc., and the diagonal line of the photograph is drawn. This is an average value obtained by extracting 12 points of fibers in the vicinity at random, removing the thickest fiber and the thinnest fiber, and measuring the remaining 10 points.
- SEM Sccanning Electron Microscope
- Scanning Electron Microscope Scanning Electron
- the blending amount of the cellulose nanofibers in the printed wiring board material of this embodiment is preferably 0.1 to 80% by mass, more preferably 0.2 to 70% by mass with respect to the total amount of the composition excluding the solvent. It is.
- the blending amount of the cellulose nanofiber is 0.1% by mass or more, the desired effect of this aspect can be obtained satisfactorily.
- film forming property improves.
- Binder component As the binder component used in this embodiment, the same components as in the second embodiment can be used.
- Carboxyl group-containing resin Moreover, when using the printed wiring board material of this aspect as an alkali development type photo solder resist which can be developed with an alkaline aqueous solution, it is also preferable to use a carboxyl group-containing resin as a binder component. As the carboxyl group-containing resin, the same resin as in the second embodiment can be used.
- an elastomer having a functional group can be added to the printed wiring board material of this embodiment.
- Trade names for elastomers having functional groups include R-45HT, Poly bd HTP-9 (manufactured by Idemitsu Kosan Co., Ltd.), Eporide PB3600 (manufactured by Daicel Corporation), Denarex R-45EPT (Nagase ChemteX Corporation) Manufactured), Ricon 130, Ricon 131, Ricon 134, Ricon 142, Ricon 150, Ricon 152, Ricon 153, Ricon 154, Ricon 156, Ricon 157, Ricon 100, Ricon 181, Ricon 184, Ricon 130MA 13013 , Ricon 131MA5, Ricon 131MA10, Ricon 131MA17, Ricon 131MA20, R con 184MA6, Ricon 156MA17 (manufactured by Sartomer Corp.) include, it can be used polyester elasto
- a resin in which a part or all of epoxy groups of epoxy resins having various skeletons are modified with carboxylic acid-modified butadiene-acrylonitrile rubber at both ends can be used.
- epoxy-containing polybutadiene elastomers, acrylic-containing polybutadiene elastomers, hydroxyl group-containing polybutadiene elastomers, hydroxyl group-containing isoprene elastomers, and the like can also be used. These elastomers may be used alone or in combination of two or more.
- thermosetting catalyst As other components, a thermosetting catalyst, a photopolymerization initiator, a colorant, and an organic solvent may be added.
- a thermosetting catalyst As these curing catalyst, photopolymerization initiator, colorant and organic solvent, those mentioned in the second embodiment can be used.
- additives such as a defoaming and leveling agent, a thixotropy imparting agent / thickening agent, a coupling agent, a dispersant, and a flame retardant, may be included as necessary.
- a defoaming and leveling agent such as a defoaming and leveling agent, a thixotropy imparting agent / thickening agent, a coupling agent, a dispersant, and a flame retardant
- the antifoaming agent / leveling agent, thixotropy imparting agent / thickening agent, coupling agent, dispersant, and flame retardant those mentioned in the first embodiment can be used.
- ingredients include photoacid generators such as diazonium salts, sulfonium salts, iodonium salts, photobase generators such as carbamate compounds, ⁇ -aminoketone compounds, O-acyloxime compounds, barium sulfate, spherical silica, hydrotalcite.
- photoacid generators such as diazonium salts, sulfonium salts, iodonium salts
- photobase generators such as carbamate compounds, ⁇ -aminoketone compounds, O-acyloxime compounds, barium sulfate, spherical silica, hydrotalcite.
- inorganic fillers such as silicon powder, nylon powder and fluorine powder, radical scavengers, ultraviolet absorbers, antioxidants, peroxide decomposers, adhesion promoters, rust inhibitors and the like.
- the printed wiring board material according to this aspect of the configuration as described above can be suitably applied to the solder resist and the core material, and can be suitably used for the interlayer insulating material of the multilayer printed wiring board, Thereby, in the obtained printed wiring board, the expected effect of this aspect can be acquired. Furthermore, when this embodiment is applied to a printed wiring board material, for example, there is a method of forming a prepreg by forming the cellulose nanofibers into a sheet shape, impregnating the sheet-like cellulose nanofibers with a binder component, and drying. Can be used.
- the multilayer printed wiring board according to this embodiment as shown in FIG. 1 can be manufactured in the same manner as in the second embodiment.
- the printed wiring board material of this embodiment can contain cellulose nanofibers produced from lignocellulose and having a number average fiber diameter of 3 nm to 1000 nm (hereinafter also referred to as lignocellulose nanofibers) and a binder component.
- cellulose nanofibers can be obtained as follows.
- Lignocellulose that exists in nature has a three-dimensional network hierarchical structure in which cellulose is tightly bound to lignin and hemicellulose. Cellulose molecules in the cell wall are not single molecules but regularly agglomerate to collect dozens of them. Crystalline microfibrils (cellulose nanofibers) are formed.
- the lignocellulose used in this embodiment can be obtained from, for example, woody biomass obtained from plants such as wood, agricultural products, vegetation, and cotton, or bacterial cellulose produced by microorganisms. In order to produce cellulose nanofibers from lignocellulose, a method of mechanically grinding in the presence of a medium can be used.
- Such mechanical pulverization methods include, for example, a ball mill (vibrating ball mill, rotating ball mill, planetary ball mill), rod mill, bead mill, disk mill, cutter mill, hammer mill, impeller mill, extruder, mixer (high-speed rotating blade mixer, Homogenizer), homogenizer (high pressure homogenizer, mechanical homogenizer, ultrasonic homogenizer) and the like.
- pulverization is preferably performed by a ball mill, a rod mill, a bead mill, a disk mill, a cutter mill, an extruder or a mixer.
- the medium used in the pulverization step is not particularly limited, but water, a low molecular compound, a high molecular compound, fatty acids, and the like are preferably used. These may be used alone or in combination of two or more. Among these, it is preferable to mix water and a low molecular compound, a high molecular compound, or fatty acids, and to use as a pulverization medium.
- examples of the low molecular weight compound include alcohols, ethers, ketones, sulfoxides, amides, amines, aromatics, morpholines, ionic liquids, and the like.
- examples of the polymer compound include alcohol polymers, ether polymers, amide polymers, amine polymers, aromatic polymers, and the like.
- examples of fatty acids include saturated fatty acids and unsaturated fatty acids. In this case, it is preferable to use water-soluble compounds as the low molecular compounds, polymer compounds and fatty acids to be used.
- ozone treatment as a pretreatment may be performed in order to facilitate pulverization.
- the number average fiber diameter of the cellulose nanofiber used in this embodiment needs to be 3 nm to 1000 nm, preferably 3 nm to 200 nm, and more preferably 3 nm to 100 nm. Since the minimum diameter of cellulose nanofiber single fiber is 3 nm, less than 3 nm cannot be manufactured substantially, and when the number average fiber diameter exceeds 1000 nm, it is excessive to obtain the desired effect of this embodiment. It is necessary to add, and film forming property deteriorates. In addition, the number average fiber diameter of the cellulose nanofiber is observed with SEM (Scanning Electron Microscope; Scanning Electron Microscope), TEM (Transmission Electron Microscope; Transmission Electron Microscope), etc., and the diagonal line of the photograph is drawn. This is an average value obtained by extracting 12 points of fibers in the vicinity at random, removing the thickest fiber and the thinnest fiber, and measuring the remaining 10 points.
- SEM Sccanning Electron Microscope
- Scanning Electron Microscope Scanning Electron
- the blending amount of the cellulose nanofibers in the printed wiring board material of this embodiment is preferably 0.1 to 80% by mass, more preferably 0.2 to 0.2% by weight based on the total amount of the composition excluding the organic solvent described later. 70% by mass.
- the blending amount of the cellulose nanofiber is 0.1% by mass or more, the desired effect of this aspect can be obtained satisfactorily.
- film forming property improves.
- Binder component As the binder component used in this embodiment, the same components as in the second embodiment can be used.
- Carboxyl group-containing resin Moreover, when using the printed wiring board material of this aspect as an alkali development type photo solder resist which can be developed with an alkaline aqueous solution, it is also preferable to use a carboxyl group-containing resin as a binder component. As the carboxyl group-containing resin, the same resin as in the second embodiment can be used.
- Examples of other conventional compounding components include a curing catalyst, a photopolymerization initiator, a colorant, and an organic solvent.
- a curing catalyst a photopolymerization initiator, a colorant, and an organic solvent.
- photopolymerization initiator, colorant and organic solvent those mentioned in the second embodiment can be used.
- additives such as a defoaming and leveling agent, a thixotropy imparting agent / thickening agent, a coupling agent, a dispersant, and a flame retardant, may be included as necessary.
- a defoaming and leveling agent such as a defoaming and leveling agent, a thixotropy imparting agent / thickening agent, a coupling agent, a dispersant, and a flame retardant
- the antifoaming agent / leveling agent, thixotropy imparting agent / thickening agent, coupling agent, dispersant, and flame retardant those mentioned in the first embodiment can be used.
- ingredients include photoacid generators such as diazonium salts, sulfonium salts, iodonium salts, photobase generators such as carbamate compounds, ⁇ -aminoketone compounds, O-acyloxime compounds, barium sulfate, spherical silica, hydrotalcite.
- photoacid generators such as diazonium salts, sulfonium salts, iodonium salts
- photobase generators such as carbamate compounds, ⁇ -aminoketone compounds, O-acyloxime compounds, barium sulfate, spherical silica, hydrotalcite.
- inorganic fillers such as silicon powder, nylon powder and fluorine powder, radical scavengers, ultraviolet absorbers, peroxide decomposers, thermal polymerization inhibitors, adhesion promoters, rust inhibitors and the like.
- the printed wiring board material according to this aspect of the configuration as described above can be suitably applied to the solder resist and the core material, and can be suitably used for the interlayer insulating material of the multilayer printed wiring board, Thereby, in the obtained printed wiring board, the expected effect of this aspect can be acquired.
- the printed wiring board material of this embodiment is applied to a core material, for example, the cellulose nanofiber is formed into a sheet shape, and a binder component is impregnated into the sheet-like cellulose nanofiber and dried to prepare a prepreg.
- a manufacturing method can be used.
- the multilayer printed wiring board according to this embodiment as shown in FIG. 1 can be manufactured in the same manner as in the second embodiment.
- tetrahydrophthalic anhydride was added to the OH group of the resin obtained above at 95 to 105 ° C. for 8 hours at a molar ratio of 0.26. This was taken out after cooling to obtain a solution containing 50% by mass (nonvolatile content) of a carboxyl group-containing resin having a solid acid value of 78.1 mgKOH / g and a mass average molecular weight of 35,000.
- Photocurable compound 1 Bisphenol A type epoxy acrylate Mitsubishi Chemical Corporation * 1-7)
- Photocurable compound 2 Trimethylolpropane triacrylate * 1-8)
- Photocurable compound 3 Kayamar PM2 Nippon Kayaku Co., Ltd. * 1-9)
- Photocurable compound 4 Light Ester HO Kyoeisha Chemical Co., Ltd. * 1-10)
- Photopolymerization initiator 1 2-ethylanthraquinone
- Curing catalyst 2 Finely pulverized melamine (manufactured by Nissan Chemical Co., Ltd.) * 1-12) Curing catalyst 3: Dicyandiamide * 1-13) Photopolymerization initiator 2: Irgacure 907 manufactured by BASF * 1-14) Acrylate: Dipentaerythritol tetraacrylate * 1-15) Epoxy compound: TEPIC-H (Nissan Chemical Co., Ltd.)
- Test substrate 1 Using a FR-4 copper-clad laminate (copper thickness 70 ⁇ m) having a size of 100 mm ⁇ 150 mm and a thickness of 1.6 mm, a line having a width of 1 mm, a length of 100 mm, and a space of 5 mm by an etching method. The pattern of was produced.
- Test substrate 2 Using a FR-4 copper-clad laminate (copper thickness 18 ⁇ m) with a size of 100 mm ⁇ 150 mm and a thickness of 1.6 mm, a 300 ⁇ m wide, 100 mm long line, 3 mm space by etching method The pattern of was produced.
- Test substrate 3 Using an FR-4 copper-clad laminate (copper thickness 9 ⁇ m) with a size of 100 mm ⁇ 150 mm and a thickness of 1.6 mm, an IPC standard B pattern comb-shaped electrode pattern was formed by an etching method. Produced.
- each component was blended, stirred, and dispersed with a three roll to prepare a solder resist composition.
- surface shows a mass part.
- compositions of Examples 1-1 to 1-3 and Comparative Example 1-1 were printed on the test substrate 1 by a screen printing method using a 100 mesh polyester bias plate in a pattern that could cover all lines. .
- a test piece was prepared by heating and curing at 140 ° C. for 30 minutes in a hot-air circulating drying oven.
- a test piece was prepared in the same manner using a 350 mesh tetron bias plate for the test substrate 2.
- a 100-mesh tetron bias plate was used for the test substrate 3, and a test piece was prepared so as to cover the comb-shaped electrode by the same method.
- compositions of Examples 1-4 to 1-6 and Comparative Example 1-2 were printed on the test substrate 1 by a screen printing method using a 100 mesh polyester bias plate in a pattern that could cover all lines. .
- an integrated light amount of 2 J / cm 2 was irradiated with a metal halide lamp at a wavelength of 350 nm and cured to prepare a test piece.
- a test piece was prepared in the same manner using a 350 mesh tetron bias plate for the test substrate 2.
- a 100-mesh tetron bias plate was used for the test substrate 3, and a test piece was prepared so as to cover the comb-shaped electrode by the same method.
- compositions of Examples 1-7 to 1-15 and Comparative Examples 1-3 to 1-5 were printed on the entire surface of the test substrate 1 using a 100 mesh polyester bias plate by a screen printing method. It was dried at 80 ° C. for 30 minutes in a drying furnace. Next, using a negative pattern that can cover all lines, exposure is performed with an integrated light quantity of 700 mJ / cm 2 with an exposure machine HMW-680GW (manufactured by Oak Manufacturing Co., Ltd.) for printed wiring boards, and 1% at 30 ° C. Using a sodium carbonate aqueous solution as a developer, development was performed for 60 seconds with a developing machine for printed wiring boards, followed by heat curing at 150 ° C.
- test pieces were prepared in the same manner using a 350 mesh tetron bias plate for the test substrate 2. Furthermore, a 100-mesh tetron bias plate was used for the test substrate 3, and a test piece was prepared so as to cover the comb-shaped electrode by the same method.
- each test piece coated with rosin-based flux was allowed to flow in a solder bath set at 260 ° C. for 60 seconds, washed with propylene glycol monomethyl ether acetate, dried, and then subjected to a peel test using a cellophane adhesive tape. The presence or absence of peeling of the coating film was confirmed.
- the evaluation criteria are as follows. The evaluation results are shown in the following table. (Evaluation) ⁇ : The coating film does not peel at all. X: The film is peeled off.
- the necessary thickness can be secured even in a state where the coating thickness becomes thin, such as a circuit thickness becoming thick, and accordingly, heat resistance and acid resistance are ensured. It is possible to prevent deterioration of characteristics such as. Moreover, electrical insulation and surface hardness were also obtained, and it was confirmed that it has sufficient characteristics as a solder resist.
- Example 2 [Production of evaluation sheet]
- each component was blended, stirred, and dispersed by a three roll to prepare each composition.
- the addition amount of the cellulose nanofiber and the layered silicate was 10% by mass with respect to the total amount of the composition excluding the solvent.
- this composition was printed on a copper foil having a thickness of 18 ⁇ m on the entire surface by a screen printing method, and cured in a hot air circulation type drying furnace at 140 ° C. for 30 minutes. Thereafter, the copper foil was removed to prepare a sheet having a thickness of 50 ⁇ m.
- Thermosetting compound 1 Epicoat 828 Mitsubishi Chemical Corporation * 2-2)
- Thermosetting compound 2 Epicoat 807 Mitsubishi Chemical Corporation * 2-3)
- Curing catalyst 1 2MZ-A Shikoku Kasei Kogyo Co., Ltd. * 2-4)
- Colorant Phthalocyanine Blue * 2-5)
- Layered silicate Lucentite STN Coop Chemical Co., Ltd. * 2-6)
- Organic solvent Carbitol acetate
- each component was blended, stirred, and dispersed with a three roll to prepare each composition.
- the addition amount of the cellulose nanofiber and the layered silicate was 10% by mass with respect to the total amount of the composition excluding the solvent.
- this composition was printed on a copper foil having a thickness of 18 ⁇ m on the entire surface by a screen printing method, dried in a hot air circulation drying oven at 100 ° C. for 30 minutes, and then at 170 ° C. for 60 minutes. And cured. Thereafter, the copper foil was removed, and the linear expansion coefficient of the obtained sheet having a thickness of 50 ⁇ m was measured.
- Thermosetting compound 3 Unidic V-8000 (solid content 40% by mass) manufactured by DIC Corporation * 2-8)
- Thermosetting compound 4 Denacol EX-830 manufactured by Nagase ChemteX Corporation * 2-9) Curing catalyst 2: Triphenylphosphine
- Each component was blended according to the description in Table 16 below, and melt kneaded at 180 ° C. for 10 minutes at a rotation speed of 70 rpm using a kneader (Laboplast Mill, manufactured by Toyo Seiki Co., Ltd.).
- the addition amount of the cellulose nanofiber and the layered silicate was 10% by mass with respect to the total amount of the composition excluding the solvent.
- the obtained kneaded product was hot-pressed at 190 ° C., 0.5 MPa for 3 minutes, and 20 MPa for 1 minute using a press machine (Lab Press P2-30T, manufactured by Toyo Seiki Co., Ltd.). Cold pressing was performed at 0.5 MPa for 1 minute.
- the linear expansion coefficient of the obtained sheet having a thickness of 50 ⁇ m was measured.
- Thermoplastic resin 1 Novatec PP BC03L manufactured by Nippon Polypro Co., Ltd.
- each component was blended and melt-kneaded at 150 ° C. for 10 minutes at a rotation speed of 70 rpm using a kneader (laboplast mill, manufactured by Toyo Seiki Co., Ltd.).
- the addition amount of the cellulose nanofiber and the layered silicate was 10% by mass with respect to the total amount of the composition excluding the solvent.
- the obtained kneaded product was hot-pressed at 160 ° C., 0.5 MPa for 3 minutes, and 20 MPa for 1 minute using a press machine (Lab Press P2-30T, manufactured by Toyo Seiki Co., Ltd.), and further at 23 ° C., Cold pressing was performed at 0.5 MPa for 1 minute.
- the linear expansion coefficient of the obtained sheet having a thickness of 50 ⁇ m was measured.
- Thermoplastic resin 2 Novatec LD LC561, manufactured by Nippon Polyethylene Co., Ltd.
- each component was blended, stirred, and dispersed with a three roll to prepare each composition.
- the addition amount of the cellulose nanofiber and the layered silicate was 10% by mass with respect to the total amount of the composition excluding the solvent.
- this composition was printed on a copper foil having a thickness of 18 ⁇ m on the entire surface by a screen printing method, dried in a hot air circulating drying oven at 120 ° C. for 10 minutes, and then at 250 ° C. for 30 minutes. And cured. Thereafter, the copper foil was removed, and the linear expansion coefficient of the obtained sheet having a thickness of 50 ⁇ m was measured.
- Thermoplastic resin 3 Socsea SOXR-OB Varnish manufactured by Nippon Kogyo Paper Industries Co., Ltd. (solid content: 70% by mass)
- each component was blended, stirred, and dispersed with a three roll to prepare each composition.
- the addition amount of the cellulose nanofiber and the layered silicate was 10% by mass with respect to the total amount of the composition excluding the solvent.
- this composition was printed on a copper foil having a thickness of 18 ⁇ m on the entire surface by a screen printing method, and cured by irradiating an integrated light amount of 2 J / cm 2 at a wavelength of 350 nm with a metal halide lamp. Thereafter, the copper foil was removed, and the linear expansion coefficient of the obtained sheet having a thickness of 50 ⁇ m was measured.
- Photo-curable compound 1 Bisphenol A type epoxy acrylate * 2-14)
- Photo-curable compound 2 Trimethylolpropane triacrylate * 2-15)
- Photo-curable compound 3 Kayamar PM2 Nippon Kayaku Co., Ltd. * 2-16)
- Photocurable compound 4 Light ester HO Kyoeisha Chemical Co., Ltd. * 2-17)
- Photopolymerization initiator 1 2-ethylanthraquinone
- each component was blended, stirred, and dispersed with a three roll to prepare each composition.
- the addition amount of the cellulose nanofiber and the layered silicate was 10% by mass with respect to the total amount of the composition excluding the solvent.
- this composition was printed on a copper foil having a thickness of 18 ⁇ m on the entire surface by a screen printing method, and dried at 80 ° C. for 30 minutes in a hot air circulation drying furnace.
- the printed wiring board exposure machine HMW-680GW manufactured by Oak Manufacturing Co., Ltd. is exposed with an integrated light amount of 700 mJ / cm 2 and 1% at 30 ° C.
- the aqueous sodium carbonate solution was developed for 60 seconds with a developing machine for printed wiring boards, and the edge portion was removed. Subsequently, thermosetting was performed at 150 ° C. for 60 minutes in a hot air circulation drying oven. Thereafter, the copper foil was removed, and the linear expansion coefficient of the obtained sheet having a thickness of 50 ⁇ m was measured.
- Curing catalyst 3 Finely pulverized melamine * 2-19) Curing catalyst 4: Dicyandiamide * 2-20) Photopolymerization initiator 2: Irgacure 907 manufactured by BASF * 2-21) Hikari Curing compound 5: Dipentaerythritol tetraacrylate * 2-22) Thermosetting compound 5: TEPIC-H Nissan Chemical Co., Ltd.
- Thermosetting compound 1 Epicoat 828, manufactured by Mitsubishi Chemical Corporation * 3-3)
- Thermosetting compound 2 Epicoat 807, manufactured by Mitsubishi Chemical Corporation * 3-3)
- Curing catalyst 1 2MZ-A * 3-4)
- Fluorine compound 1 Megafac RS-75 (solid content 40 mass) %) DIC Corporation * 3-9) Fluorine Compound 2: Asahi Guard AG-E300D (solid content 30% by mass) Asahi Glass Co., Ltd. * 3-10) Organic Solvent: Carbitol Acetate
- Thermosetting compound 3 Unidic V-8000 (solid content 40% by mass) manufactured by DIC Corporation * 3-12)
- Thermosetting compound 4 Denacol EX-830 manufactured by Nagase ChemteX Corporation * 3-13)
- Thermosetting compound 5 TEPIC-H, Nissan Chemical Co., Ltd. * 3-14)
- Thermoplastic resin 1 Novatec PPBC03L, Nippon Polypro Co., Ltd.
- Thermoplastic resin 2 Novatec LDLC561 * 3-16) Thermoplastic resin 3 manufactured by Nippon Polyethylene Co., Ltd .: Socsea SOXR-OB (solid content 70% by mass) Varnish manufactured by Nippon Kogyo Paper Industries Co., Ltd. * 3-17) Photo-curable compound 1: Bisphenol A Type epoxy acrylate manufactured by Mitsubishi Chemical Co., Ltd. * 3-18) Photocurable compound 2: Trimethylolpropane triacrylate * 3-19) Photocurable compound 3: Kayamer PM2 Nippon Kayaku Co., Ltd. * 3-20) Photocurable Compound 4: Light Ester HO Kyoeisha Chemical Co., Ltd.
- Photocurable Compound 5 Dipentaerythritol Tetraacrylate * 3-22 )
- Curing catalyst 2 Triphenylphosphine * 3-23)
- Curing catalyst 3 Finely ground melamine * 3-24)
- Curing catalyst 4 Dicyandiamide * 3-25)
- Photopolymerization initiator 1 2-ethyl Anthraquinone * 3-26)
- Photopolymerization initiator 2 Irgacure 907 manufactured by BASF
- each component was blended and used at 180 ° C. for 10 minutes using a kneader (laboroplast mill, manufactured by Toyo Seiki Co., Ltd.) Melt kneading was performed at a rotation speed of 70 rpm.
- the obtained kneaded product was hot-pressed at 190 ° C., 0.5 MPa for 3 minutes, and 20 MPa for 1 minute using a press machine (Lab Press P2-30T, manufactured by Toyo Seiki Co., Ltd.), and further at 23 ° C., 0 Cooled and pressed at 5 MPa for 1 minute.
- FIG. 2 is an explanatory view showing a method for producing a substrate for evaluating an interlayer insulating material.
- (a) to (e-1) are plan views
- (e-2) is a sectional view of (e-1).
- the compositions of Example 3-1 to Example 3-13 were prepared from an FR having a size of 50 mm ⁇ 50 mm and a thickness of 1.6 mm, in which a conductor layer 21a was provided on an insulating layer 21b.
- test board 21 of copper-clad laminate (with copper pad, copper thickness 18 ⁇ m) by screen printing, and cured in a hot air circulating drying oven at 140 ° C for 30 minutes for insulation Resin layer 22 was formed.
- a hole (via) 23 having a diameter of 100 ⁇ m is formed on the conductor layer 21a with a carbon dioxide laser, and then smear is removed with an aqueous potassium permanganate solution, followed by electroless copper plating and then electrolytic copper plating on the entire surface.
- the plating layer 24 was formed.
- the test piece was produced by forming the wiring pattern 26 by the etching method.
- Reference numeral 25 in the figure indicates an etching resist pattern.
- Example 3-14, Example 3-22 and Example 3-24 were printed on the entire surface of the test substrate by the screen printing method, and the conditions were 100 ° C. and 30 minutes in a hot air circulating drying oven. And dried at 170 ° C. for 60 minutes. Next, a test piece was prepared by forming a wiring pattern in the same manner as described above.
- Sheet-like cellulose nanofiber having a thickness of 0.05 mm comprising Reference Example 3-1, Reference Example 3-2, Reference Example 3-4, Reference Example 3-5, Comparative Example 3-1 and Comparative Example 3-2
- the composite molded body was hot-pressed on the test substrate at 190 ° C. and 20 MPa for 1 minute, and further cold-pressed at 23 ° C. and 0.5 MPa for 1 minute.
- a test piece was prepared by forming a wiring pattern in the same manner as described above.
- compositions of Reference Example 3-3, Reference Example 3-6, and Comparative Example 3-3 were printed on the entire surface of the test substrate by a screen printing method, and were heated at 120 ° C. for 10 minutes in a hot air circulating drying oven. After drying, it was cured at 250 ° C. for 30 minutes. Next, a test piece was prepared by forming a wiring pattern in the same manner as described above.
- Example 3-15, Example 3-20 and Example 3-25 were printed on the entire surface of the test substrate by screen printing, and accumulated at 2 J / cm 2 at a wavelength of 350 nm using a metal halide lamp. Light was irradiated and cured. Next, a test piece was prepared by forming a wiring pattern in the same manner as described above.
- Example 3-16 to Example 3-18, Example 3-21 to Example 3-23, and Example 3-26 to Example 3-28 were printed on the entire surface by screen printing. Then, it was dried in a hot air circulation drying oven at 80 ° C. for 30 minutes. Next, using a negative pattern that can cover the edge of the test substrate, the printed wiring board exposure machine HMW-680GW (manufactured by Oak Manufacturing Co., Ltd.) is exposed with an integrated light amount of 700 mJ / cm 2 and 1% at 30 ° C. A developing solution for a printed wiring board was used for 60 seconds by using a sodium carbonate aqueous solution as a developing solution, and the edges were then thermally cured at 150 ° C. for 60 minutes in a hot air circulating drying oven. Next, a test piece was prepared by forming a wiring pattern in the same manner as described above.
- Example 3-29 50 parts by mass of Epicoat 828 manufactured by Mitsubishi Chemical Corporation, 50 parts by mass of Epicoat 807 manufactured by Mitsubishi Chemical Corporation, 3 parts by mass of 2MZ-A manufactured by Shikoku Kasei Kogyo Co., Ltd., Big Chemie Japan Co., Ltd. 2 parts by mass of BYK-313 manufactured by the manufacturer and 100 parts by mass of methyl ethyl ketone were blended and stirred to prepare a resin solution. This was impregnated into each cellulose nanofiber sheet, left in an atmosphere at 50 ° C. for 12 hours, then taken out and dried at 80 ° C. for 5 hours to prepare a prepreg.
- a copper foil having a thickness of 18 ⁇ m was stacked on the front and back, and cured for 3 hours in a vacuum press at a temperature of 160 ° C. and a pressure of 2 MPa.
- a through hole 27 having a drill diameter of 300 ⁇ m is formed by drilling in the laminated plate 21 made of the insulating layer 21b having the conductor layer 21a formed on both surfaces thereof. , With a pitch of 5 mm. Thereafter, smear was removed with an aqueous potassium permanganate solution, electroless copper plating treatment, and then electrolytic copper plating treatment were performed to form through holes 28.
- the wiring pattern 26 was produced by an etching method to obtain a test piece.
- Example 3-30 50 parts by mass of Epicoat 828 manufactured by Mitsubishi Chemical Corporation, 50 parts by mass of Epicoat 807 manufactured by Mitsubishi Chemical Corporation, 3 parts by mass of 2MZ-A manufactured by Shikoku Kasei Kogyo Co., Ltd., manufactured by DIC Corporation
- a test piece was obtained in the same manner as in Example 3-29, except that 0.75 parts by mass of MegaFac RS-75 and 100 parts by mass of methyl ethyl ketone were mixed and stirred to prepare a resin solution.
- Example 3-4 50 parts by mass of Epicoat 828 manufactured by Mitsubishi Chemical Corporation, 50 parts by mass of Epicoat 807 manufactured by Mitsubishi Chemical Corporation, 3 parts by mass of 2MZ-A manufactured by Shikoku Chemicals Co., Ltd., and 100 parts by mass of methyl ethyl ketone
- a test piece was obtained in the same manner as in Example 3-29 except that a resin solution was prepared by mixing a part.
- Example 3-31 100 parts by mass of Unidic V-8000 manufactured by DIC Corporation, 23 parts by mass of Denacol EX-830 manufactured by Nagase ChemteX Corporation, 1 part by mass of triphenylphosphine, BYK manufactured by BYK Japan Japan Co., Ltd.
- a test piece was obtained in the same manner as in Example 3-29 except that 2 parts by mass of -313 and 100 parts by mass of methyl ethyl ketone were mixed and stirred to prepare a resin solution.
- Example 3-32 100 parts by weight of Unidic V-8000 manufactured by DIC Corporation, 23 parts by weight of Denacor EX-830 manufactured by Nagase ChemteX Corporation, 1 part by weight of triphenylphosphine, MegaFac RS manufactured by DIC Corporation A test piece was obtained in the same manner as in Example 3-29 except that 0.75 part by mass of -75 and 100 parts by mass of methyl ethyl ketone were mixed and stirred to prepare a resin solution.
- Example 3-5 100 parts by weight of Unidic V-8000 manufactured by DIC Corporation, 23 parts by weight of Denacol EX-830 manufactured by Nagase ChemteX Corporation, 1 part by weight of triphenylphosphine, and 100 parts by weight of methyl ethyl ketone A test piece was obtained in the same manner as in Example 3-29 except that a resin solution was prepared by stirring.
- Example 3-6 Test piece as in Example 3-29 except that 100 parts by weight of Socsea SOXR-OB manufactured by Nippon Kogyo Paper Industries Co., Ltd. and 70 parts by weight of methyl ethyl ketone were mixed and stirred to prepare a resin solution. Got.
- the wiring pattern 26 was produced by an etching method to obtain a test piece.
- Reference Example 3-10 A test piece was prepared in the same manner as Reference Example 3-9, except that the 0.5 mm thick sheet of Reference Example 3-4 was used.
- Comparative Example 3-7 A test piece was prepared in the same manner as Reference Example 3-9, except that the 0.5 mm thick sheet of Comparative Example 3-1 was used.
- Reference Example 3-11 A test piece was prepared in the same manner as Reference Example 3-9, except that the 0.5 mm thick sheet of Reference Example 3-2 was used.
- Reference Example 3-12 A test piece was produced in the same manner as Reference Example 3-9, except that the 0.5 mm thick sheet of Reference Example 3-5 was used.
- Comparative Example 3-8 A test piece was prepared in the same manner as Reference Example 3-9 except that the 0.5 mm thick sheet of Comparative Example 3-2 was used.
- Example 4 [Preparation of cellulose fiber dispersion] Softwood kraft pulp (NBKP) is mechanically treated with a high-pressure homogenizer, and the resulting cellulose fiber with a number average fiber diameter of 3 ⁇ m is added to water and stirred sufficiently to produce an aqueous suspension of 10% by weight cellulose fiber. did. This was subjected to dehydration filtration, 10 times the amount of carbitol acetate as the weight of the filtrate was added, and the mixture was stirred for 30 minutes and then filtered. This substitution operation was repeated three times, and 10 times the amount of carbitol acetate by weight of the filtrate was added to prepare a 10% by mass cellulose fiber dispersion.
- NNKP Softwood kraft pulp
- each component was blended, stirred, and dispersed with a three roll to prepare each composition.
- the obtained composition was printed on the entire surface of a FR-4 copper-clad laminate (copper thickness 18 ⁇ m) having a size of 150 mm ⁇ 100 mm and a thickness of 1.6 mm by a screen printing method. Curing was carried out at 30 ° C. for 30 minutes. The film thickness after curing was 50 ⁇ m. Thereafter, the surface of the cured product was roughened with an aqueous potassium permanganate solution, and electroless copper plating and then electrolytic copper plating were applied to the entire surface to prepare an evaluation substrate.
- Thermosetting compound 1 Epicote 828, manufactured by Mitsubishi Chemical Corporation * 4-2)
- Thermosetting compound 2 Epicote 807, manufactured by Mitsubishi Chemical Corporation * 4-3)
- Curing catalyst 1 2MZ-A * 4-4)
- Colorant Phthalocyanine Blue * 4-5)
- Organic solvent Carbitol acetate
- each component was blended, stirred, and dispersed with a three roll to prepare each composition.
- the obtained composition was printed on the entire surface of a FR-4 copper-clad laminate (copper thickness 18 ⁇ m) having a size of 150 mm ⁇ 100 mm and a thickness of 1.6 mm by a screen printing method. After drying at 30 ° C. for 30 minutes, it was cured at 170 ° C. for 60 minutes. The film thickness after curing was 50 ⁇ m. Thereafter, the surface of the cured product was roughened with an aqueous potassium permanganate solution, and electroless copper plating and then electrolytic copper plating were applied to the entire surface to prepare an evaluation substrate.
- Thermosetting compound 3 Unidic V-8000 (solid content 40% by mass) manufactured by DIC Corporation * 4-7)
- Thermosetting compound 4 Denacol EX-830 manufactured by Nagase ChemteX Corporation * 4-8) Curing catalyst 2: Triphenylphosphine
- each component was blended and melt-kneaded at 180 ° C. for 10 minutes at a rotation speed of 70 rpm using a kneader (laboplast mill, manufactured by Toyo Seiki Co., Ltd.).
- the obtained kneaded product was hot-pressed at 190 ° C., 0.5 MPa for 3 minutes, and 20 MPa for 1 minute using a press machine (Lab Press P2-30T, manufactured by Toyo Seiki Co., Ltd.). Cold pressing was performed at 0.5 MPa for 1 minute.
- a sheet having a thickness of 50 ⁇ m was obtained.
- This sheet was hot-pressed on a FR-4 copper-clad laminate (copper thickness 18 ⁇ m) having a size of 150 mm ⁇ 100 mm and a thickness of 1.6 mm by hot pressing at 190 ° C. and 20 MPa for 1 minute, and further at 23 ° C.
- a test piece was produced by cold pressing at 0.5 MPa for 1 minute. Thereafter, the surface of the cured product was roughened with an aqueous potassium permanganate solution, and electroless copper plating and then electrolytic copper plating were applied to the entire surface to prepare an evaluation substrate.
- Thermoplastic resin 1 Novatec PP BC03L manufactured by Nippon Polypro Co., Ltd.
- each component was blended and melt-kneaded at 150 ° C. for 10 minutes at a rotation speed of 70 rpm using a kneader (laboplast mill, manufactured by Toyo Seiki Co., Ltd.).
- the obtained kneaded product was hot-pressed at 160 ° C., 0.5 MPa for 3 minutes, and 20 MPa for 1 minute using a press machine (Lab Press P2-30T, manufactured by Toyo Seiki Co., Ltd.), and further at 23 ° C., Cold pressing was performed at 0.5 MPa for 1 minute.
- a sheet having a thickness of 50 ⁇ m was obtained.
- This sheet was hot-pressed on a FR-4 copper-clad laminate (copper thickness: 18 ⁇ m) having a size of 150 mm ⁇ 100 mm and a thickness of 1.6 mm by hot pressing at 190 ° C. and 20 MPa for 1 minute.
- a test piece was produced by cooling and pressing at 5 MPa for 1 minute. Thereafter, the surface of the cured product was roughened with an aqueous potassium permanganate solution, and electroless copper plating and then electrolytic copper plating were applied to the entire surface to prepare an evaluation substrate.
- Thermoplastic resin 2 Novatec LDLC561 Made by Nippon Polyethylene Co., Ltd.
- each component was blended, stirred, and dispersed with a three roll to prepare each composition.
- the obtained composition was printed on the entire surface of a FR-4 copper-clad laminate (copper thickness 18 ⁇ m) having a size of 150 mm ⁇ 100 mm and a thickness of 1.6 mm by a screen printing method, and 120 ° C. in a hot air circulation drying oven. After drying at 10 ° C. for 10 minutes, it was cured at 250 ° C. for 30 minutes. The film thickness after curing was 50 ⁇ m.
- the surface of the cured product was roughened with an aqueous potassium permanganate solution, and electroless copper plating and then electrolytic copper plating were applied to the entire surface to prepare an evaluation substrate. Cut the copper plated part into a 10mm wide and 100mm long part, peel off one end of the copper plated part, grab it with a gripping tool, and peel off 35mm vertically at a speed of 50mm / min at room temperature (Peel strength) was measured.
- Thermoplastic resin 3 Socsea SOXR-OB Varnish manufactured by Nippon Kogyo Paper Industry Co., Ltd. (solid content: 70% by mass)
- each component was blended, stirred, and dispersed with a three roll to prepare each composition.
- the obtained composition was printed on the entire surface of a FR-4 copper-clad laminate (copper thickness 18 ⁇ m) having a size of 150 mm ⁇ 100 mm and a thickness of 1.6 mm by a screen printing method, and a wavelength of 350 nm using a metal halide lamp.
- a metal halide lamp was irradiated with an integrated light amount of 2 J / cm 2 and cured.
- the film thickness after curing was 50 ⁇ m.
- the surface of the cured product was roughened with an aqueous potassium permanganate solution, and electroless copper plating and then electrolytic copper plating were applied to the entire surface to prepare an evaluation substrate. Cut the copper plated part into a 10mm wide and 100mm long part, peel off one end of the copper plated part, grab it with a gripping tool, and peel off 35mm vertically at a speed of 50mm / min at room temperature (Peel strength) was measured.
- Photocurable compound 1 Bisphenol A type epoxy acrylate Mitsubishi Chemical Corporation * 4-13)
- Photocurable compound 2 Trimethylolpropane triacrylate * 4-14)
- Photocurable compound 3 Kayamar PM2 Nippon Kayaku Co., Ltd. * 4-15)
- Photocurable Compound 4 Light Ester HO Kyoeisha Chemical Co., Ltd. * 4-16)
- Photopolymerization initiator 1 2-ethylanthraquinone
- each component was blended, stirred, and dispersed with a three roll to prepare each composition.
- the obtained composition was printed on the entire surface of a FR-4 copper-clad laminate (copper thickness: 18 ⁇ m) having a size of 150 mm ⁇ 100 mm and a thickness of 1.6 mm by a screen printing method. , And dried at 80 ° C. for 30 minutes.
- the printed wiring board exposure machine HMW-680GW manufactured by Oak Manufacturing Co., Ltd.
- HMW-680GW manufactured by Oak Manufacturing Co., Ltd.
- aqueous sodium carbonate solution as a developer, development was performed with a printed wiring board developing machine for 60 seconds, and then the edges were thermally cured at 150 ° C. for 60 minutes in a hot-air circulating drying furnace. The film thickness after curing was 50 ⁇ m. Thereafter, the surface of the cured product was roughened with an aqueous potassium permanganate solution, and electroless copper plating and then electrolytic copper plating were applied to the entire surface to prepare an evaluation substrate. Cut the copper plated part into a 10mm wide and 100mm long part, peel off one end of the copper plated part, grab it with a gripping tool, and peel off 35mm vertically at a speed of 50mm / min at room temperature (Peel strength) was measured.
- Curing catalyst 3 Finely pulverized melamine * 4-18) Curing catalyst 4: Dicyandiamide * 4-19) Photopolymerization initiator 2: Irgacure 907 manufactured by BASF * 4-20) Light Curing compound 5: Dipentaerythritol tetraacrylate * 4-21) Thermosetting compound 5: TEPIC-H Nissan Chemical Co., Ltd.
- Example 5 [Production of Cellulose Nanofiber Dispersion Having Carboxylate] (Production Example 1) 2, 2, 6, 6 5 g of softwood bleached kraft pulp (manufactured by Oji Paper Co., Ltd., moisture 50% by mass, Canadian standard freeness (CSF) 550 ml, mainly in an absolutely dry state with a number average fiber diameter exceeding 1000 nm) -Tetramethylpiperidine-N-oxyl (TEMPO) 79 mg (0.5 mmol) and sodium bromide 515 mg (5 mmol) were added to 500 ml of an aqueous solution and stirred until the pulp was uniformly dispersed.
- CSF Canadian standard freeness
- TEMPO Tetramethylpiperidine-N-oxyl
- distilled water was added to the reaction product to obtain an aqueous dispersion having a pulp concentration of 2% by mass, and the mixture was stirred and dispersed with a rotary blade mixer for 5 minutes. Since the viscosity of the slurry significantly increased with stirring, distilled water was added little by little, and stirring and dispersion with a mixer was continued until the solid content concentration reached 0.2% by mass to obtain a transparent gelled aqueous solution. This was observed with TEM and confirmed to be an aqueous dispersion of cellulose nanofibers having a carboxylate having a number average fiber diameter of 10 nm. The amount of carboxyl groups in the aqueous dispersion was 1.25 mmol / g.
- Thermosetting compound 1 Epicoat 828, manufactured by Mitsubishi Chemical Corporation * 5-2)
- Thermosetting compound 2 Epicoat 807, manufactured by Mitsubishi Chemical Corporation * 5-3)
- Curing catalyst 1 2MZ-A Shikoku Kasei Kogyo Co., Ltd. * 5-4)
- Colorant Phthalocyanine Blue * 5-5)
- Organic solvent Carbitol acetate
- Thermoset 1 compound 3 Unidic V-8000 manufactured by DIC Corporation (solid content 40% by mass) * 5-7)
- Thermosetting compound 4 Denacol EX-830, manufactured by Nagase ChemteX Corporation * 5-8)
- Curing catalyst 2 Triphenylphosphine
- Thermoplastic resin 1 Socsea SOXR-OB Varnish manufactured by Nippon Kogyo Paper Industries Co., Ltd. (solid content 70% by mass, N-methylpyrrolidone 30% by mass)
- Photocurable compound 1 Bisphenol A type epoxy acrylate Mitsubishi Chemical Corporation * 5-11
- Photocurable compound 2 Trimethylolpropane triacrylate * 5-12
- Photocurable compound 3 Kayamar PM2 Nippon Kayaku Co., Ltd. * 5-13
- Photocurable Compound 4 Light Ester HO Kyoeisha Chemical Co., Ltd. * 5-14)
- Photopolymerization initiator 1 2-ethylanthraquinone
- Curing catalyst 3 Finely pulverized melamine * 5-16) Curing catalyst 4: Dicyandiamide * 5-17) Photopolymerization initiator 2: Irgacure 907 manufactured by BASF * 5-18) Photocuring Compound 5: dipentaerythritol tetraacrylate * 5-19) thermosetting compound 5: TEPIC-H manufactured by Nissan Chemical Co., Ltd.
- each component was blended, stirred, and dispersed with a three roll to prepare each composition.
- this composition was printed on a copper foil having a thickness of 18 ⁇ m on the entire surface by a screen printing method, and cured in a hot air circulation type drying furnace at 140 ° C. for 30 minutes. Thereafter, the copper foil was removed to prepare an evaluation sheet having a thickness of 50 ⁇ m.
- each component was blended, stirred, and dispersed with a three roll to prepare each composition.
- this composition was printed on a copper foil having a thickness of 18 ⁇ m on the entire surface by a screen printing method, dried in a hot air circulation drying oven at 100 ° C. for 30 minutes, and then at 170 ° C. for 60 minutes. And cured. Thereafter, the copper foil was removed to prepare an evaluation sheet having a thickness of 50 ⁇ m.
- each component was blended, stirred, and dispersed with a three roll to prepare each composition.
- this composition was printed on a copper foil having a thickness of 18 ⁇ m on the entire surface by a screen printing method, dried in a hot air circulating drying oven at 120 ° C. for 10 minutes, and then at 250 ° C. for 30 minutes. And cured. Thereafter, the copper foil was removed to prepare an evaluation sheet having a thickness of 50 ⁇ m.
- each component was blended, stirred, and dispersed with a three roll to prepare each composition.
- this composition was printed on a copper foil having a thickness of 18 ⁇ m on the entire surface by a screen printing method, and cured by irradiating an integrated light amount of 2 J / cm 2 at a wavelength of 350 nm with a metal halide lamp. Thereafter, the copper foil was removed to prepare an evaluation sheet having a thickness of 50 ⁇ m.
- each component was blended, stirred, and dispersed with a three roll to prepare each composition.
- this composition was printed on a copper foil having a thickness of 18 ⁇ m on the entire surface by a screen printing method, and dried at 80 ° C. for 30 minutes in a hot air circulation drying furnace.
- the printed wiring board exposure machine HMW-680GW manufactured by Oak Manufacturing Co., Ltd.
- HMW-680GW manufactured by Oak Manufacturing Co., Ltd.
- the aqueous sodium carbonate solution was developed for 60 seconds with a developing machine for printed wiring boards, and the copper foil edge was removed. Subsequently, it was cured at 150 ° C. for 60 minutes in a hot air circulating drying oven. Thereafter, the copper foil was removed to prepare an evaluation sheet having a thickness of 50 ⁇ m.
- the crack resistance can be improved by using a printed wiring board material containing cellulose nanofibers having a carboxylate.
- Thermosetting compound 1 Epicoat 828, manufactured by Mitsubishi Chemical Corporation * 6-2)
- Thermosetting compound 2 Epicoat 807, manufactured by Mitsubishi Chemical Corporation * 6-3)
- Curing catalyst 1 2MZ-A * 6-4)
- Pigment phthalocyanine blue * 6-5)
- Organic solvent Carbitol acetate
- Thermosetting compound 3 Unidic V-8000 manufactured by DIC Corporation (solid content 40% by mass) * 6-7)
- Thermosetting compound 4 Denacol EX-830, manufactured by Nagase ChemteX Corporation * 6-8)
- Curing catalyst 2 Triphenylphosphine
- Thermoplastic resin 1 Novatec PP BC03L manufactured by Nippon Polypro Co., Ltd.
- Thermoplastic resin 2 Novatec LD LC561, manufactured by Nippon Polyethylene Co., Ltd.
- Thermoplastic resin 3 Socsea SOXR-OB Varnish manufactured by Nippon Kogyo Paper Industries Co., Ltd. (solid content 70% by mass, N-methylpyrrolidone 30% by mass)
- Photocurable compound 1 bisphenol A type epoxy acrylate Mitsubishi Chemical Corporation * 6-13)
- Photocurable compound 2 Trimethylolpropane triacrylate * 6-14)
- Photocurable compound 3 Kayamar PM2 Nippon Kayaku Co., Ltd. * 6-15)
- Photocurable compound 4 Light ester HO Kyoeisha Chemical Co., Ltd. * 6-16)
- Photopolymerization initiator 1 2-ethylanthraquinone
- Curing catalyst 3 Finely pulverized melamine (manufactured by Nissan Chemical Co., Ltd.) * 6-18) Curing catalyst 4: Dicyandiamide * 6-19) Photopolymerization initiator 2: Irgacure 907 (BASF) * 6-20) Photocurable compound 5: Dipentaerythritol tetraacrylate * 6-21) Thermosetting compound 5: TEPIC-H (manufactured by Nissan Chemical Co., Ltd.)
- Example 6-1 to 6-7 and Comparative Example 6-1 were printed by a screen printing method so as to cover the comb-shaped electrodes, and a hot-air circulating drying furnace And cured at 140 ° C. for 30 minutes to prepare a test piece.
- a withstand voltage test a DC voltage was applied to each of the six test pieces at a boosting speed of 500 V / second to measure the breakdown voltage.
- the case where the average of 6 sheets was 4.5 kV or more was evaluated as ⁇ , and the case where it was less than 4.5 kV was evaluated as ⁇ .
- the results of Examples 6-1 to 6-6 were all “good”, and those of Example 6-7 and Comparative Example 6-1 were all “x”.
- Example 6-8 to 6-14 and Comparative Example 6-2 were printed by a screen printing method so as to cover the comb-shaped electrodes, and a hot-air circulating drying oven And dried at 100 ° C. for 30 minutes and then cured at 170 ° C. for 60 minutes to prepare a test piece.
- a DC voltage was applied to each of the six test pieces at a boosting speed of 500 V / second to measure the breakdown voltage. The case where the average of 6 sheets was 5.5 kV or more was evaluated as ⁇ , and the case where it was less than 5.5 kV was evaluated as x.
- the 0.05 mm thick sheets of Reference Example 6-1 to Reference Example 6-12 and Comparative Example 6-3 to Comparative Example 6-6 were cut and processed so as to cover the comb-shaped electrode. Then, hot pressing was performed at 190 ° C. and 20 MPa for 1 minute by hot pressing, and further cooling pressing was performed at 23 ° C. and 0.5 MPa for 1 minute to prepare a test piece. As a withstand voltage test, a DC voltage was applied to each of the six test pieces at a boosting speed of 500 V / second to measure the breakdown voltage. The case where the average of 6 sheets was 3.5 kV or more was evaluated as ⁇ , and the case where it was less than 3.5 kV was evaluated as ⁇ .
- the compositions of Reference Examples 6-13 to 6-18 and Comparative Examples 6-7 and 6-8 were printed by the screen printing method so as to cover the comb electrodes, After drying at 120 ° C. for 10 minutes in a circulation drying furnace, the test piece was cured by curing at 250 ° C. for 30 minutes. As a withstand voltage test, a DC voltage was applied to each of the six test pieces at a boosting speed of 500 V / second to measure the breakdown voltage. The case where the average of 6 sheets was 5.5 kV or more was evaluated as ⁇ , and the case where it was less than 5.5 kV was evaluated as x. The results of Reference Examples 6-13 to 6-18 were all “good”, and those of Comparative Examples 6-7 and 6-8 were all “x”.
- Example 6-15 to 6-21 and Comparative Example 6-9 were printed by the screen printing method so as to cover the comb-shaped electrode, and then a metal halide lamp A test piece was prepared by irradiating and curing an integrated light amount of 2 J / cm 2 at a wavelength of 350 nm.
- a withstand voltage test a DC voltage was applied to each of the six test pieces at a boosting speed of 500 V / second to measure the breakdown voltage. The case where the average of 6 sheets was 3.5 kV or more was evaluated as ⁇ , and the case where it was less than 3.5 kV was evaluated as ⁇ .
- Examples 6-15 to 6-20 were all “good”, and those of Example 6-21 and Comparative example 6-9 were all “x”.
- a DC voltage of 50 V was applied to each of six test pieces, a standing test was performed in an atmosphere of 130 ° C. and 85% RH, and the time until short-circuiting was measured.
- the case where the average of 6 sheets was 100 hours or more was evaluated as ⁇ , and the case where it was less than 100 hours was evaluated as ⁇ .
- the results of Examples 6-15 to 6-20 were all “good”, and those of Example 6-21 and Comparative example 6-9 were all “x”.
- compositions of Examples 6-22 to 6-42 and Comparative Examples 6-10 to 6-12 were screen-printed on the entire surface using a 100 mesh polyester bias plate. Printed and dried in a hot air circulating drying oven at 80 ° C. for 30 minutes. Next, using a negative pattern that can be covered with a comb-shaped electrode, exposure is performed with an integrated light quantity of 700 mJ / cm 2 with an exposure machine HMW-680GW (manufactured by Oak Manufacturing Co., Ltd.) for printed wiring boards, and 1% at 30 ° C. Using a sodium carbonate aqueous solution as a developer, development was performed for 60 seconds with a developing machine for printed wiring boards, followed by heat curing at 150 ° C.
- test pieces For 60 minutes in a hot-air circulating drying furnace to prepare test pieces.
- a withstand voltage test a DC voltage was applied to each of the six test pieces at a boosting speed of 500 V / second to measure the breakdown voltage.
- the case where the average of 6 sheets was 4.5 kV or more was evaluated as ⁇ , and the case where it was less than 4.5 kV was evaluated as ⁇ .
- the results of Examples 6-22 to 6-34 and Examples 36 to 41 are all “good”, and the results of Example 35, Example 42, Comparative Example 6-10 to Comparative Example 6-12 are good.
- Everything was x.
- a DC voltage of 50 V was applied to each of six test pieces, a standing test was performed in an atmosphere of 130 ° C.
- Example 6-1 to Example 6-7 and Comparative Example 6-1 were applied to an FR-4 copper-clad laminate (copper thickness 9 ⁇ m) having a size of 100 mm ⁇ 150 mm and a thickness of 1.6 mm. It printed on the whole surface by the screen-printing method, and it hardened
- a DC voltage was applied to each of the six test pieces at a boosting speed of 500 V / second to measure the breakdown voltage.
- a DC voltage of 50 V was applied to each of six test pieces, a standing test was performed in an atmosphere of 130 ° C. and 85% RH, and the time until short-circuiting was measured.
- Example 6-8 to Example 6-14 and Comparative Example 6-2 was applied to an FR-4 copper-clad laminate (copper thickness 9 ⁇ m) having a size of 100 mm ⁇ 150 mm and a thickness of 1.6 mm.
- the entire surface was printed by a screen printing method, dried in a hot air circulation drying oven at 100 ° C. for 30 minutes, and then cured at 170 ° C. for 60 minutes.
- electroless copper plating was applied, and then electrolytic copper plating was applied. Thereafter, a test piece having an IPC standard B pattern comb-shaped electrode pattern was produced by an etching method.
- a DC voltage was applied to each of the six test pieces at a boosting speed of 500 V / second to measure the breakdown voltage.
- a DC voltage of 50 V was applied to each of six test pieces, a standing test was performed in an atmosphere of 130 ° C. and 85% RH, and the time until short-circuiting was measured.
- the average of 6 sheets was evaluated as “ ⁇ ” when the average was 500 hours or more, and “ ⁇ ” when the average was less than 500 hours.
- the results of Examples 6-8 to 6-13 were all “good”, and those of examples 6-14 and comparative example 6-2 were all “x”.
- the sheets of Reference Example 6-1 to Reference Example 6-12 and Comparative Example 6-3 to Comparative Example 6-6 having a thickness of 0.05 mm are FR-4 having a size of 100 mm ⁇ 150 mm and a thickness of 1.6 mm.
- a copper-clad laminate (copper thickness 9 ⁇ m) was hot-pressed by hot pressing at 190 ° C. and 20 MPa for 1 minute, and further cold-pressed by 23 ° C. and 0.5 MPa for 1 minute. Next, electroless copper plating was applied, and then electrolytic copper plating was applied. Thereafter, a test piece having an IPC standard B pattern comb-shaped electrode pattern was produced by an etching method.
- a DC voltage was applied to each of the six test pieces at a boosting speed of 500 V / second to measure the breakdown voltage.
- a DC voltage of 50 V was applied to each of six test pieces, a standing test was performed in an atmosphere of 130 ° C. and 85% RH, and the time until short-circuiting was measured.
- compositions of Reference Example 6-13 to Reference Example 6-18 and Comparative Examples 6-7 and 6-8 were combined with an FR-4 copper-clad laminate (copper thickness of 100 mm ⁇ 150 mm and 1.6 mm thickness). 9 ⁇ m) was printed on the entire surface by a screen printing method, dried in a hot air circulation drying oven at 120 ° C. for 10 minutes, and then cured at 250 ° C. for 30 minutes. Next, electroless copper plating was applied, and then electrolytic copper plating was applied. Thereafter, a test piece having an IPC standard B pattern comb-shaped electrode pattern was produced by an etching method.
- a DC voltage was applied to each of the six test pieces at a boosting speed of 500 V / second to measure the breakdown voltage.
- a DC voltage of 50 V was applied to each of six test pieces, a standing test was performed in an atmosphere of 130 ° C. and 85% RH, and the time until short-circuiting was measured.
- Example 6-15 to Example 6-21 and Comparative Example 6-9 was applied to an FR-4 copper-clad laminate (copper thickness 9 ⁇ m) having a size of 100 mm ⁇ 150 mm and a thickness of 1.6 mm.
- the entire surface was printed by a screen printing method, and then cured by irradiating an integrated light amount of 2 J / cm 2 at a wavelength of 350 nm with a metal halide lamp.
- electroless copper plating was applied, and then electrolytic copper plating was applied. Thereafter, a test piece having an IPC standard B pattern comb-shaped electrode pattern was produced by an etching method.
- a DC voltage was applied to each of the six test pieces at a boosting speed of 500 V / second to measure the breakdown voltage.
- a DC voltage of 50 V was applied to each of six test pieces, a standing test was performed in an atmosphere of 130 ° C. and 85% RH, and the time until short-circuiting was measured.
- compositions of Examples 6-22 to 6-42 and Comparative Examples 6-10 to 6-12 were combined with FR-4 copper-clad laminate (100 mm ⁇ 150 mm and 1.6 mm thick).
- a copper mesh thickness of 9 ⁇ m) was printed on the entire surface by screen printing using a 100 mesh polyester bias plate and dried in a hot air circulation drying oven at 80 ° C. for 30 minutes.
- the printed wiring board exposure machine HMW-680GW (Oak Manufacturing Co., Ltd.) was exposed with an integrated light amount of 700 mJ / cm 2 and 1% at 30 ° C.
- aqueous sodium carbonate solution as a developing solution, development was performed with a developing machine for printed wiring boards for 60 seconds, followed by heat curing at 150 ° C. for 60 minutes in a hot air circulation drying oven. Next, electroless copper plating was applied, and then electrolytic copper plating was applied. Thereafter, a test piece having an IPC standard B pattern comb-shaped electrode pattern was produced by an etching method. As a withstand voltage test, a DC voltage was applied to each of the six test pieces at a boosting speed of 500 V / second to measure the breakdown voltage. The case where the average of 6 sheets was 5.5 kV or more was evaluated as ⁇ , and the case where it was less than 5.5 kV was evaluated as x.
- Examples 6-22 to 6-34 and Examples 6-36 to 6-41 are all “good”, and Examples 6-35, 6-42 and Comparative Example 6-
- the values of 10 to Comparative Examples 6-12 were all x.
- a DC voltage of 50 V was applied to each of six test pieces, a standing test was performed in an atmosphere of 130 ° C. and 85% RH, and the time until short-circuiting was measured. The case where the average of 6 sheets was 400 hours or more was evaluated as “ ⁇ ”, and the case where it was less than 400 hours was evaluated as “X”.
- the results of Examples 6-22 to 6-34 and Examples 6-36 to 6-41 are all “good”, and Examples 6-35, 6-42 and Comparative Example 6-
- the values of 10 to Comparative Examples 6-12 were all x.
- lignocellulose nanofiber sheet (Preparation of lignocellulose nanofiber sheet) About lignocellulose nanofiber dispersion liquid 1 and lignocellulose nanofiber dispersion liquid 2, a 0.2% by mass dispersion liquid is prepared with carbitol acetate, filtered through a glass filter, and has a size of 100 mm ⁇ 150 mm and a thickness of 40 ⁇ m. A sheet was produced.
- Example 6-43 the test piece of lignocellulose nanofiber dispersion 2 was Example 6-44
- the test piece of cellulose nanofiber dispersion 1 was Example 6-45
- a glass cloth was used instead of cellulose nanofiber, and a similar product was prepared as Comparative Examples 6-13.
- Example 6-43, Example 6-44, Example 6-45, and Comparative Example 6-13 the filling ratio of the cellulose fiber was 30% by mass.
- a DC voltage was applied to each of the six test pieces at a boosting speed of 500 V / second to measure the breakdown voltage.
- a DC voltage of 50 V was applied to each of six test pieces, a standing test was performed in an atmosphere of 130 ° C. and 85% RH, and the time until short-circuiting was measured.
- test piece having an IPC standard B pattern comb-shaped electrode pattern was produced by an etching method.
- the test piece of lignocellulose nanofiber dispersion 1 was Example 6-46
- the test piece of lignocellulose nanofiber dispersion 2 was Example 6-47
- the test piece of cellulose nanofiber dispersion 1 was Example 6-48
- a glass cloth was used instead of the cellulose nanofiber, and a similar product was made as Comparative Example 6-14.
- the packing ratio of the cellulose fibers was 30% by mass.
- a DC voltage was applied to each of the six test pieces at a boosting speed of 500 V / second to measure the breakdown voltage.
- the test piece of lignocellulose nanofiber dispersion 1 was Reference Example 6-19
- the test piece of lignocellulose nanofiber dispersion 2 was Reference Example 6-20
- the test piece of cellulose nanofiber dispersion 1 was Comparative Example 6-15
- a glass cloth was used instead of cellulose nanofiber, and a similar product was made as Comparative Example 6-16.
- the filling rate of cellulose fibers in Reference Example 6-19, Reference Example 6-20, Comparative Example 6-15, and Comparative Example 6-16 was 30% by mass.
- a withstand voltage test a DC voltage was applied to each of the six test pieces at a boosting speed of 500 V / second to measure the breakdown voltage.
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Abstract
Description
[本発明の第一の態様]
本発明のソルダーレジスト組成物は、硬化性樹脂と、数平均繊維径3nm~1000nmのセルロースナノファイバーと、を含む点に特徴を有するものである。かかるセルロースナノファイバーは、以下のようにして得ることができる。
セルロースナノファイバーの原材料としては、木材や麻、竹、綿、ジュート、ケナフ、ビート、農産物残廃物、布等の天然植物繊維原料から得られるパルプ、レーヨンやセロファン等の再生セルロース繊維等を用いることができ、中でも特に、パルプが好適である。パルプとしては、植物原料を化学的若しくは機械的に、または、両者を併用してパルプ化することにより得られるクラフトパルプや亜硫酸パルプ等のケミカルパルプ、セミケミカルパルプ、ケミグランドパルプ、ケミメカニカルパルプ、サーモメカニカルパルプ、ケミサーモメカニカルパルプ、リファイナーメカニカルパルプ、砕木パルプおよびこれらの植物繊維を主成分とする脱墨古紙パルプ、雑誌古紙パルプ、段ボール古紙パルプなどを用いることができる。中でも、繊維の強度が強い針葉樹由来の各種クラフトパルプ、例えば、針葉樹未漂白クラフトパルプ、針葉樹酸素晒し未漂白クラフトパルプ、針葉樹漂白クラフトパルプが特に好適である。
本発明に用いる硬化性樹脂としては、熱硬化性樹脂および光硬化性樹脂のうちから選択されるものが好適であり、これらの混合物であってもよい。
(式中、R1は、水素原子または炭素数1~6のアルキル基を示す)により表されるオキセタン環を含有するオキセタン化合物の具体例としては、3-エチル-3-ヒドロキシメチルオキセタン(東亞合成(株)製、商品名OXT-101)、3-エチル-3-(フェノキシメチル)オキセタン(東亞合成(株)製、商品名OXT-211)、3-エチル-3-(2-エチルヘキシロキシメチル)オキセタン(東亞合成(株)製、商品名OXT-212)、1,4-ビス{[(3-エチル-3-オキセタニル)メトキシ]メチル}ベンゼン(東亞合成(株)製、商品名OXT-121)、ビス(3-エチル-3-オキセタニルメチル)エーテル(東亞合成(株)製、商品名OXT-221)などが挙げられる。さらに、フェノールノボラックタイプのオキセタン化合物なども挙げられる。これらオキセタン化合物は、上記エポキシ化合物と併用してもよく、また、単独で使用してもよい。
また、本発明のソルダーレジスト組成物をアルカリ現像型の感光性樹脂組成物とする場合には、カルボキシル基含有樹脂を含有することが好ましい。カルボキシル基含有樹脂は、エチレン性不飽和基を有するカルボキシル基含有感光性樹脂であってもよい。
(1)不飽和カルボン酸と不飽和二重結合を有する化合物との共重合によって得られるカルボキシル基含有樹脂、および、それを変性して分子量や酸価を調整したカルボキシル基含有樹脂。
(2)カルボキシル基含有(メタ)アクリル系共重合樹脂に1分子中にオキシラン環とエチレン性不飽和基を有する化合物を反応させて得られる感光性のカルボキシル基含有樹脂。
(3)1分子中にそれぞれ1個のエポキシ基および不飽和二重結合を有する化合物と不飽和二重結合を有する化合物との共重合体に不飽和モノカルボン酸を反応させ、この反応により生成した第2級の水酸基に飽和または不飽和多塩基酸無水物を反応させて得られる感光性のカルボキシル基含有樹脂。
(4)水酸基含有ポリマーに飽和または不飽和多塩基酸無水物を反応させた後、この反応により生成したカルボン酸に1分子中にそれぞれ1個のエポキシ基および不飽和二重結合を有する化合物を反応させて得られる感光性の水酸基およびカルボキシル基含有樹脂。
(5)多官能エポキシ化合物と不飽和モノカルボン酸とを反応させ、この反応により生成した第2級の水酸基の一部または全部に多塩基酸無水物を反応させて得られる感光性のカルボキシル基含有樹脂。
(6)多官能エポキシ化合物と、1分子中に2個以上の水酸基およびエポキシ基と反応する水酸基以外の1個の反応基を有する化合物と、不飽和基含有モノカルボン酸とを反応させ、得られた反応生成物に多塩基酸無水物を反応させて得られるカルボキシル基含有感光性樹脂。
(7)フェノール性水酸基をもつ樹脂とアルキレンオキシドまたは環状カーボネートとの反応生成物に不飽和基含有モノカルボン酸を反応させ、得られた反応生成物に多塩基酸無水物を反応させて得られるカルボキシル基含有感光性樹脂。
(8)多官能エポキシ化合物と、1分子中に少なくとも1個のアルコール性水酸基および1個のフェノール性水酸基を有する化合物と、不飽和基含有モノカルボン酸とを反応させ、得られた反応生成物のアルコール性水酸基に対して多塩基酸無水物の無水物基を反応させて得られるカルボキシル基含有感光性樹脂。
本発明のソルダーレジスト組成物において、光硬化性樹脂ないしカルボキシル基含有感光性樹脂を用いる場合には、さらに、光重合開始剤を添加することが好ましい。光重合開始剤としては、例えば、ベンゾイン、ベンゾインメチルエ-テル、ベンゾインエチルエ-テル、ベンゾインイソプロピルエ-テル、ベンゾインイソブチルエ-テル、ベンジルメチルケタ-ルなどのベンゾイン化合物とそのアルキルエ-テル類;アセトフェノン、2,2-ジメトキシ-2-フェニルアセトフェノン、2-ヒドロキシ-2-メチル-1-フェニルプロパン-1-オン、ジエトキシアセトフェノン、2,2-ジエトキシ-2-フェニルアセトフェノン、1,1-ジクロロアセトフェノン、1-ヒドロキシシクロヘキシルフェニルケトン、2-メチル-1-[4-(メチルチオ)フェニル]-2-モルフォリノ-プロパン-1-オンなどのアセトフェノン類;メチルアントラキノン、2-エチルアントラキノン、2-ターシャリ-ブチルアントラキノン、1-クロロアントラキノン、2-アミルアントラキノンなどのアントラキノン類;チオキサントン、2、4-ジエチルチオキサントン、2-クロロチオキサントン、2,4-ジクロロチオキサントン、2-メチルチオキサントン、2,4-ジイソプロピルチオキサントンなどのチオキサントン類;アセトフェノンジメチルケタ-ル、ベンジルジメチルケタ-ルなどのケタ-ル類;ベンゾフェノン、4,4-ビスメチルアミノベンゾフェノンなどのベンゾフェノン類などが挙げられる。これらは単独または2種類以上を混合して使用することが可能であり、さらに、トリエタノ-ルアミン、メチルジエタノ-ルアミン等の第3級アミン;2-ジメチルアミノエチル安息香酸、4-ジメチルアミノ安息香酸エチルなどの安息香酸誘導体などの光重合開始助剤等と組み合わせて使用することができる。
また、本発明のソルダーレジスト組成物において、熱硬化性樹脂を用いる場合は、さらに、硬化剤および/または硬化触媒を添加することができる。
慣用の他の配合成分として、例えば、熱硬化成分としては、エピスルフィド樹脂や、メラミン誘導体、ベンゾグアナミン誘導体等のアミノ樹脂、ポリイソシアネート化合物、またはブロックイソシアネート化合物が挙げられる。
また、着色剤として、着色顔料や染料等としてカラーインデックスで表される公知慣用のものが使用可能である。例えば、Pigment Blue 15、15:1、15:2、15:3、15:4 15:6、16、60、Solvent Blue 35、63、68、70、83、87、94、97、122、136、67、70、Pigment Green 7、36、3、5、20、28、Solvent Yellow 163、Pigment Yellow 24、108、193、147、199、202、110、109、139 179 185 93、94、95、128、155、166、180、120、151、154、156、175、181、1、2、3、4、5、6、9、10、12、61、62、62:1、65、73、74、75、97、100、104、105、111、116、167、168、169、182、183、12、13、14、16、17、55、63、81、83、87、126、127、152、170、172、174、176、188、198、Pigment Orange 1、5、13、14、16、17、24、34、36、38、40、43、46、49、51、61、63、64、71、73、Pigment Red 1、2、3、4、5、6、8、9、12、14、15、16、17、21、22、23、31、32、112、114、146、147、151、170、184、187、188、193、210、245、253、258、266、267、268、269、37、38、41、48:1、48:2、48:3、48:4、49:1、49:2、50:1、52:1、52:2、53:1、53:2、57:1、58:4、63:1、63:2、64:1、68、171、175、176、185、208、123、149、166、178、179、190、194、224、254、255、264、270、272、220、144、166、214、220、221、242、168、177、216、122、202、206、207、209、Solvent Red 135、179、149、150、52、207、Pigment Violet 19、23、29、32、36、38、42、Solvent Violet 13、36、Pigment Brown 23、25、Pigment Black 1、7等が挙げられる。
消泡剤・レベリング剤としては、シリコーン、変性シリコーン、鉱物油、植物油、脂肪族アルコール、脂肪酸、金属石鹸、脂肪酸アミド、ポリオキシアルキレングリコール、ポリオキシアルキレンアルキルエーテル、ポリオキシアルキレン脂肪酸エステル等の化合物等が使用できる。
本態様のプリント配線板材料は、バインダー成分と、数平均繊維径3nm~1000nmのセルロースナノファイバーと、層状珪酸塩と、を含むものとすることができる。
本態様で用いられるバインダー成分としては、熱可塑性樹脂、および、熱硬化性樹脂や光硬化性樹脂などの硬化性樹脂を好適に用いることができる。
カルボキシル基含有樹脂としては、感光性の不飽和二重結合を1個以上有する感光性のカルボキシル基含有樹脂、および、感光性の不飽和二重結合を有しないカルボキシル基含有樹脂のいずれも使用可能であり、特定のものに限定されるものではない。カルボキシル基含有樹脂としては、第一の態様において挙げた樹脂を好適に使用することができる。
消泡剤・レベリング剤、カップリング剤、分散剤、難燃剤としては、第一の態様で挙げたものを用いることができる。
本態様のプリント配線板材料は、バインダー成分と、数平均繊維径3nm~1000nmのセルロースナノファイバーと、シリコーン化合物およびフッ素化合物のうちのいずれか一方または双方と、を含むものとすることができる。
上記シリコーン化合物としては、ポリジメチルシロキサン、ポリアルキルフェニルシロキサン、アルキル変性シリコーンオイル、ポリエーテル変性シリコーンオイル、ポリアルキルシロキサン、ポリメチルシルセスキオキサン、ポリアルキル水素シロキサン、ポリアルキルアルケニルシロキサン、ポリメチルフェニルシロキサン、アラルキル変性シリコーンオイル、アルキルアラルキル変性シリコーンオイルなどが挙げられる。市販品としては、BYK-300、BYK-302、BYK-306、BYK-307、BYK-310、BYK-313、BYK-330、BYK-331、BYK-333、BYK-337、BYK-341、BYK-344、BYK-370、BYK375(以上、ビックケミー・ジャパン(株)製)、KS-66、KS-69、FZ-2110、FZ-2166、FZ-2154、FZ-2120、L-720、L-7002、SH8700、L-7001、FZ-2123、SH8400、FZ-77、FZ-2164、FZ-2203、FZ-2208(以上、東レ・ダウコーニング(株)製)、KF-353、KF-615A、KF-640、KF-642、KF-643、KF-6020、X-22-6191、KF-6011、KF-6015、X-22-2516、KF-410、X-22-821、KF-412、KF-413、KF-4701(以上、信越化学(株)製)が挙げられる。
上記フッ素化合物としては、例えば、分子中にパーフルオロアルキル基やパーフルオロアルケニル基などを有するフッ素系樹脂を挙げることができる。市販品としては、例えばメガファックF-444、同F-472、同F-477、同F-552、同F-553、同F-554、同F-443、同F-470、同F-470、同F-475、同F-482、同F-483、同F-489、同R-30、同RS-75(以上、DIC(株)製)、エフトップEF301、同303、同352(以上 新秋田化成(株)製)、フロラードFC-430、同FC-431(以上、住友スリーエム(株)製)、アサヒガードAG-E300D、サーフロンS-382、同SC-101、同SC-102、同SC-103、同SC-104、同SC-105、同SC-106(以上、旭硝子(株)製)、BM-1000、BM-1100(以上、裕商(株)製)、NBX-15、FTX-218(以上、(株)ネオス製)が挙げられる。
本態様で用いられるバインダー成分としては、第二の態様と同様のものを用いることができる。
また、本態様のプリント配線板材料をアルカリ水溶液で現像可能なアルカリ現像型のフォトソルダーレジストとして使用する場合には、バインダー成分としてカルボキシル基含有樹脂を使用することも好ましい。
カルボキシル基含有樹脂としては、第二の態様と同様のものを用いることができる。
これら硬化触媒、光重合開始剤、着色剤、有機溶剤としては、第二の態様で挙げたものを用いることができる。
消泡剤・レベリング剤としては、鉱物油、植物油、脂肪族アルコール、脂肪酸、金属石鹸、脂肪酸アミド、ポリオキシアルキレングリコール、ポリオキシアルキレンアルキルエーテル、ポリオキシアルキレン脂肪酸エステル等の化合物等が使用できる。
チクソトロピー付与剤・増粘剤、カップリング剤、分散剤、難燃剤としては、第一の態様で挙げたものを用いることができる。
本態様のプリント配線板材料は、バインダー成分と、数平均繊維径1μm以上のセルロースファイバーと、数平均繊維径3nm以上1000nm未満のセルロースナノファイバーと、を含むものとすることができる。
上記セルロースファイバーおよびセルロースナノファイバーは、以下のようにして得ることができる。
セルロースファイバーおよびセルロースナノファイバーの原材料としては、第一の態様と同様のものを挙げることができる。
本態様で用いられるバインダー成分としては、第二の態様と同様のものを用いることができる。
また、本態様のプリント配線板材料をアルカリ水溶液で現像可能なアルカリ現像型の絶縁材料として使用する場合には、バインダー成分としてカルボキシル基含有樹脂を使用することも好ましい。
カルボキシル基含有樹脂としては、第二の態様と同様のものを用いることができる。
これら硬化触媒、光重合開始剤、着色剤、有機溶剤としては、第二の態様で挙げたものを用いることができる。
消泡剤・レベリング剤、チクソトロピー付与剤・増粘剤、カップリング剤、分散剤、難燃剤としては、第一の態様で挙げたものを用いることができる。
本態様のプリント配線板材料は、バインダー成分と、構造中にカルボン酸塩を有する数平均繊維径3nm~1000nmのセルロースナノファイバーと、を含むものとすることができる。かかるセルロースナノファイバーは、以下に従い、天然セルロース繊維を酸化させた後、微細化することにより得ることができる。
まず、天然セルロース繊維を、絶対乾燥基準で約10~1000倍量(質量基準)の水中に、ミキサー等を用いて分散させることにより、水分散液を調製する。上記セルロースナノファイバーの原料となる天然セルロース繊維としては、例えば、針葉樹系パルプや広葉樹系パルプ等の木材パルプ、麦わらパルプやバガスパルプ等の非木材系パルプ、コットンリントやコットンリンター等の綿系パルプ、バクテリアセルロース等を挙げることができる。これらは、1種を単独で用いても、2種以上を適宜組み合わせて用いてもよい。また、これら天然セルロース繊維には、あらかじめ表面積を大きくするために叩解等の処理を施しておいてもよい。
官能基量[mmol/g]=V[ml]×0.05/セルロースナノファイバー試料[g]
本態様で用いられるバインダー成分としては、第二の態様と同様のものを用いることができる。
また、本態様のプリント配線板材料をアルカリ水溶液で現像可能なアルカリ現像型のフォトソルダーレジストとして使用する場合には、バインダー成分としてカルボキシル基含有樹脂を使用することも好ましい。
カルボキシル基含有樹脂としては、第二の態様と同様のものを用いることができる。
これら硬化触媒、光重合開始剤、着色剤、有機溶剤としては、第二の態様で挙げたものを用いることができる。
消泡剤・レベリング剤、チクソトロピー付与剤・増粘剤、カップリング剤、分散剤、難燃剤としては、第一の態様で挙げたものを用いることができる。
本態様のプリント配線板材料は、リグノセルロースから製造された数平均繊維径3nm~1000nmのセルロースナノファイバー(以下、リグノセルロースナノファイバーともいう。)と、バインダー成分とを含むものとすることができる。かかるセルロースナノファイバーは、以下のようにして得ることができる。
自然界に存在するリグノセルロースは、セルロースがリグニンおよびヘミセルロースに強固に結びついた三次元ネットワーク階層構造を有しており、細胞壁中のセルロース分子が単分子ではなく規則的に凝集して数十本集まった結晶性を有するミクロフィブリル(セルロースナノファイバー)を形成している。具体的には、本態様において使用するリグノセルロースは、例えば、木材や農産物、草木、綿花等の植物から得られる木質バイオマスや、微生物が産生するバクテリアセルロース等から得ることができる。リグノセルロースからセルロースナノファイバーを製造するためには、媒体を共存させて機械的に粉砕する方法を用いることができる。
本態様で用いられるバインダー成分としては、第二の態様と同様のものを用いることができる。
また、本態様のプリント配線板材料をアルカリ水溶液で現像可能なアルカリ現像型のフォトソルダーレジストとして使用する場合には、バインダー成分としてカルボキシル基含有樹脂を使用することも好ましい。
カルボキシル基含有樹脂としては、第二の態様と同様のものを用いることができる。
これら硬化触媒、光重合開始剤、着色剤、有機溶剤としては、第二の態様で挙げたものを用いることができる。
消泡剤・レベリング剤、チクソトロピー付与剤・増粘剤、カップリング剤、分散剤、難燃剤としては、第一の態様で挙げたものを用いることができる。
[合成例1]
(ワニス1)
攪拌機、温度計、還流冷却器、滴下ロートおよび窒素導入管を備えた2リットルセパラブルフラスコに、溶媒としてのジエチレングリコールジメチルエーテル900g、および、重合開始剤としてのt-ブチルパーオキシ2-エチルヘキサノエート(日油(株)製、商品名;パーブチルO)21.4gを加えて、90℃に加熱した。加熱後、ここに、メタクリル酸309.9g、メタクリル酸メチル116.4g、およびラクトン変性2-ヒドロキシエチルメタクリレート((株)ダイセル製、商品名;プラクセルFM1)109.8gを、重合開始剤であるビス(4-t-ブチルシクロヘキシル)パーオキシジカーボネート(日油(株)製、商品名;パーロイルTCP)21.4gとともに3時間かけて滴下して加えた。さらに、これを6時間熟成することにより、カルボキシル基含有共重合樹脂を得た。なお、これらの反応は、窒素雰囲気下で行った。
(ワニス2)
温度計、攪拌機、滴下ロート、および還流冷却器を備えたフラスコに、溶媒としてのジエチレングリコールモノエチルエーテルアセテート、および、触媒としてのアゾビスイソブチロニトリルを入れ、窒素雰囲気下、これを80℃に加熱し、メタアクリル酸とメチルメタアクリレートとを0.40:0.60のモル比で混合したモノマーを約2時間かけて滴下した。さらに、これを1時間攪拌した後、温度を115℃にまで上げ、失活させて樹脂溶液を得た。
(ワニス3)
温度計、攪拌器、滴下ロートおよび還流冷却器を備えたフラスコに、クレゾールノボラック型エポキシ樹脂(DIC(株)製、エピクロンN-680、エポキシ当量=210)210gと、溶媒としてのカルビトールアセテート96.4gとを加え、加熱溶解させた。続いて、これに、重合禁止剤としてのハイドロキノン0.1g、および、反応触媒としてのトリフェニルホスフィン2.0gを加えた。この混合物を95~105℃に加熱し、アクリル酸72gを徐々に滴下し、酸価が3.0mgKOH/g以下となるまで、約16時間反応させた。この反応生成物を80~90℃にまで冷却した後、テトラヒドロフタル酸無水物76.1gを加え、赤外吸光分析により、酸無水物の吸収ピーク(1780cm-1)がなくなるまで、約6時間反応させた。この反応溶液に、出光興産(株)製の芳香族系溶剤イプゾール#150を96.4g加え、希釈した後に取り出した。このようにして得られたカルボキシル基含有の感光性ポリマー溶液は、不揮発分が65質量%、固形分の酸価が78mgKOH/gであった。
セルロースナノファイバー((株)スギノマシン製,BiNFi-s(ビンフィス) 10質量%セルロース、数平均繊維径80nm)を脱水濾過し、濾物重量の10倍量のカルビトールアセテートを加えて、30分間攪拌した後に濾過した。この置換操作を3回繰返して、濾物重量の10倍量のカルビトールアセテートを加え、10質量%のセルロースナノファイバー分散液を作製した。
*1-2)熱硬化性化合物2:エピコート807 三菱化学(株)製
*1-3)硬化触媒1:2MZ-A 四国化成工業(株)製
*1-4)着色剤:フタロシアニンブルー
*1-5)有機溶剤:カルビトールアセテート
*1-7)光硬化性化合物2:トリメチロールプロパントリアクリレート
*1-8)光硬化性化合物3:カヤマーPM2 日本化薬(株)製
*1-9)光硬化性化合物4:ライトエステルHO 共栄社化学(株)製
*1-10)光重合開始剤1:2-エチルアントラキノン
*1-12)硬化触媒3:ジシアンジアミド
*1-13)光重合開始剤2:イルガキュア907 BASF社製
*1-14)アクリレート:ジペンタエリスリトルテトラアクリレート
*1-15)エポキシ化合物:TEPIC-H(日産化学(株)製)
(試験基板1):100mm×150mmの大きさで1.6mmの厚さのFR-4銅張り積層板(銅厚70μm)を用いて、エッチング工法により幅1mm、長さ100mmのライン、スペース5mmのパターンを作製した。
(試験基板2):100mm×150mmの大きさで1.6mmの厚さのFR-4銅張り積層板(銅厚18μm)を用いて、エッチング工法により幅300μm、長さ100mmのライン、スペース3mmのパターンを作製した。
(試験基板3):100mm×150mmの大きさで1.6mmの厚さのFR-4銅張り積層板(銅厚9μm)を用いて、エッチング工法によりIPC規格Bパターンのくし型電極のパターンを作製した。
各試験片について、ライン上の塗膜の状態を、20倍のルーペを用いて目視にて評価した。塗膜は着色しているので、色の濃淡で厚みを判断した。評価基準は以下の通りである。評価結果を下記の表中に示す。
(評価)○:ライン上に充分な厚さの塗膜がある。
△:ライン上に充分な厚さの塗膜があるが、際部分が薄くなっている。
×:ライン上の塗膜が薄い。
各試験片について、ロジン系フラックスを塗布した各試験片を、あらかじめ260℃に設定したはんだ槽に60秒間フローさせ、プロピレングリコールモノメチルエーテルアセテートで洗浄し乾燥した後、セロハン粘着テープによるピールテストを行い、塗膜の剥がれの有無を確認した。評価基準は以下の通りである。評価結果を下記の表中に示す。
(評価)○:塗膜に剥がれが全くないもの。
×:塗膜に剥がれが生じているもの。
各試験片を、10容量%の硫酸水溶液に25℃で60分浸漬させて、水洗し、乾燥させた。その後、セロハン粘着テープによるピールテストを行い、塗膜の剥がれの有無を確認した。評価基準は上記と同様である。評価結果を下記の表中に示す。
試験基板3の試験片について、くし形電極間にDC500Vのバイアスを印加し、絶縁抵抗値を測定した。値が100GΩ以上であれば○、100GΩ未満であれば×とした。結果を下記の表中に示す。
試験基板3の試験片を用いて、芯の先が平らになるように研がれたBから9Hの鉛筆を、約45°の角度で押し付けて、塗膜の剥がれが生じない鉛筆の硬さを記録した。結果を下記の表中に示す。
[評価シートの作製]
下記表14中の記載に従って、各成分を配合、攪拌して、3本ロールにて分散させて、各組成物を作製した。セルロースナノファイバーおよび層状珪酸塩の添加量は、溶剤を除く組成物の全体量に対し、それぞれ10質量%とした。次に、この組成物を、厚さ18μmの銅箔に、スクリーン印刷法にて全面に印刷し、熱風循環式乾燥炉で140℃、30分間の条件で硬化させた。その後、銅箔を除去し、厚さ50μmのシートを作製した。
前記で作製したシートを、3mm幅×30mm長にカットした。これを、SII製 TMA(Thermomechanical Analysis)「EXSTAR6000」を用いて、引張モードで、チャック間10mm、荷重30mN、窒素雰囲気下、室温から200℃まで5℃/分で昇温し、次いで、200℃から20℃まで5℃/分で降温した。その後、20℃から200℃まで5℃/分で昇温した際の30℃から100℃の測定値から、線膨張係数を求めた。評価結果を表14中に示した。
*2-2)熱硬化性化合物2:エピコート807 三菱化学(株)製
*2-3)硬化触媒1:2MZ-A 四国化成工業(株)製
*2-4)着色剤:フタロシアニンブルー
*2-5)層状珪酸塩:ルーセンタイトSTN コープケミカル(株)製
*2-6)有機溶剤:カルビトールアセテート
*2-8)熱硬化性化合物4:デナコール EX-830 ナガセケムテックス(株)製
*2-9)硬化触媒2:トリフェニルホスフィン
*2-14)光硬化性化合物2:トリメチロールプロパントリアクリレート
*2-15)光硬化性化合物3:カヤマーPM2 日本化薬(株)製
*2-16)光硬化性化合物4:ライトエステルHO 共栄社化学(株)製
*2-17)光重合開始剤1:2-エチルアントラキノン
*2-19)硬化触媒4:ジシアンジアミド
*2-20)光重合開始剤2:イルガキュア907 BASF社製
*2-21)光硬化性化合物5:ジペンタエリスリトルテトラアクリレート
*2-22)熱硬化性化合物5:TEPIC-H 日産化学(株)製
*3-2)熱硬化性化合物2:エピコート807 三菱化学(株)製
*3-3)硬化触媒1:2MZ-A 四国化成工業(株)製
*3-4)着色剤:フタロシアニンブルー
*3-5)シリコーン化合物1:BYK-313(固形分15質量%) ビックケミー・ジャパン(株)製
*3-6)シリコーン化合物2:SH-8400 東レ・ダウコーニング(株)製
*3-7)シリコーン化合物3:KS-66 信越化学(株)製
*3-8)フッ素化合物1:メガファックRS-75(固形分40質量%) DIC(株)製
*3-9)フッ素化合物2:アサヒガードAG-E300D(固形分30質量%) 旭硝子(株)製
*3-10)有機溶剤:カルビトールアセテート
*3-12)熱硬化性化合物4:デナコールEX-830 ナガセケムテックス(株)製
*3-13)熱硬化性化合物5:TEPIC-H 日産化学(株)製
*3-14)熱可塑性樹脂1:ノバテックPPBC03L 日本ポリプロ(株)製
*3-15)熱可塑性樹脂2:ノバテックLDLC561 日本ポリエチレン(株)製
*3-16)熱可塑性樹脂3:ソクシールSOXR-OB(固形分70質量%) ニッポン高度紙工業(株)製のワニス
*3-17)光硬化性化合物1:ビスフェノールA型エポキシアクリレート 三菱化学(株)製
*3-18)光硬化性化合物2:トリメチロールプロパントリアクリレート
*3-19)光硬化性化合物3:カヤマーPM2 日本化薬(株)製
*3-20)光硬化性化合物4:ライトエステルHO 共栄社化学(株)製
*3-21)光硬化性化合物5:ジペンタエリスリトルテトラアクリレート
*3-22)硬化触媒2:トリフェニルホスフィン
*3-23)硬化触媒3:微粉砕メラミン 日産化学(株)製
*3-24)硬化触媒4:ジシアンジアミド
*3-25)光重合開始剤1:2-エチルアントラキノン
*3-26)光重合開始剤2:イルガキュア907 BASF社製
(試験片の作製)
図2に、層間絶縁材の評価用基板の作製方法を示す説明図を示す。図中の(a)~(e-1)は平面図であり、(e-2)は、(e-1)の断面図である。図2に示すように、実施例3-1~実施例3-13の組成物を、絶縁層21b上に導体層21aが設けられた、50mm×50mmの大きさで厚さ1.6mmのFR-4銅張り積層板(銅パッド付、銅厚18μm)の試験基板21に、スクリーン印刷法にて全面に印刷し、熱風循環式乾燥炉で140℃、30分間の条件で硬化させて、絶縁樹脂層22を形成した。次に、炭酸ガスレーザーにて直径100μmの穴(ビア)23を導体層21a上にあけ、その後、過マンガン酸カリウム水溶液にてスミアを除去し、無電解銅めっき、次いで電解銅めっきを全面につけて、めっき層24を形成した。さらに、エッチング工法により配線パターン26を形成することで、試験片を作製した。図中の符号25は、エッチングレジストパターンを示す。
6枚の試験片の電極に50Vの直流電圧をかけて、130℃85%の雰囲気下で放置試験を行なった。試験槽内で絶縁抵抗を測定し、試験開始後1時間後の絶縁抵抗値から100分の1になった時間を記録した。100時間を過ぎても絶縁抵抗値が下がらないものはそこで終了とした。その結果を、下記の表中に示す。
(セルロースナノファイバーシートの作製)
セルロースナノファイバーについて、蒸留水にて0.2質量%水懸濁液を作製し、ガラスフィルターで濾過して成膜し、50mm×50mmの大きさで厚み40μmのシートを作製した。
三菱化学(株)製のエピコート828を50質量部、三菱化学(株)製のエピコート807を50質量部、四国化成工業(株)製の2MZ-Aを3質量部、ビックケミー・ジャパン(株)製のBYK-313を2質量部、および、メチルエチルケトンを100質量部配合し、攪拌して樹脂溶液を作製した。これを、各セルロースナノファイバーシートに含浸させて、50℃の雰囲気に12時間放置した後、取り出し、80℃、5時間乾燥させてプリプレグを作製した。このプリプレグを10枚重ね、さらに、表裏に厚み18μmの銅箔を重ねて、真空プレス機で温度160℃、圧力2MPaの条件で、3時間硬化させた。次に、図3(a)~(c)に示すように、この両面に導体層21aの形成された絶縁層21bよりなる積層板21に、ドリル加工にて、ドリル径300μmの貫通穴27を、ピッチ5mmであけた。その後、過マンガン酸カリウム水溶液にてスミアを除去し、無電解銅めっき処理、次いで、電解銅めっき処理を行い、スルーホール28を形成した。次に、図4(a)~(c)に示すように、配線パターン26をエッチング工法により作製し、試験片を得た。
三菱化学(株)製のエピコート828を50質量部、三菱化学(株)製のエピコート807を50質量部、四国化成工業(株)製の2MZ-Aを3質量部、DIC(株)製のメガファックRS-75を0.75質量部、および、メチルエチルケトンを100質量部配合し、攪拌して樹脂溶液を作製したこと以外は実施例3-29と同様に、試験片を得た。
三菱化学(株)製のエピコート828を50質量部、三菱化学(株)製のエピコート807を50質量部、四国化成工業(株)製の2MZ-Aを3質量部、および、メチルエチルケトンを100質量部配合し、攪拌して樹脂溶液を作製したこと以外は実施例3-29と同様に、試験片を得た。
DIC(株)製のユニディックV-8000を100質量部、ナガセケムテックス(株)製のデナコールEX-830を23質量部、トリフェニルホスフィンを1質量部、ビックケミー・ジャパン(株)製のBYK-313を2質量部、および、メチルエチルケトンを100質量部配合し、攪拌して樹脂溶液を作製したこと以外は実施例3-29と同様に、試験片を得た。
DIC(株)製のユニディックV-8000を100質量部、ナガセケムテックス(株)製のデナコールEX-830を23質量部、トリフェニルホスフィンを1質量部、DIC(株)製のメガファックRS-75を0.75質量部、および、メチルエチルケトンを100質量部配合し、攪拌して樹脂溶液を作製したこと以外は実施例3-29と同様に、試験片を得た。
DIC(株)製のユニディックV-8000を100質量部、ナガセケムテックス(株)製のデナコールEX-830を23質量部、トリフェニルホスフィンを1質量部、および、メチルエチルケトンを100質量部配合し、攪拌して樹脂溶液を作製したこと以外は実施例3-29と同様に、試験片を得た。
ニッポン高度紙工業(株)製のソクシールSOXR-OBを100質量部、ビックケミー・ジャパン(株)製のBYK-313を1.3質量部、および、メチルエチルケトンを70質量部配合し、攪拌して樹脂溶液を作製したこと以外は実施例3-29と同様に、試験片を得た。
ニッポン高度紙工業(株)製のソクシールSOXR-OBを100質量部、メガファックRS-75を0.5質量部、および、メチルエチルケトンを70質量部配合し、攪拌して樹脂溶液を作製したこと以外は実施例3-29と同様に、試験片を得た。
ニッポン高度紙工業(株)製のソクシールSOXR-OBを100質量部、および、メチルエチルケトンを70質量部配合し、攪拌して樹脂溶液を作製したこと以外は実施例3-29と同様に、試験片を得た。
参考例3-1の厚さ0.5mmのシート状の上記セルロースナノファイバー複合成形体の表裏に18μmの銅箔を重ねて、真空プレス機で温度190℃、圧力0.5MPaの条件で、1分間加熱した。次に、図3(a)~(c)に示すように、この両面に導体層21aの形成された絶縁層21bよりなる積層板21に、ドリル加工にて、ドリル径300μmの貫通穴27を、ピッチ5mmであけた。その後、過マンガン酸カリウム水溶液にてスミアを除去し、無電解銅めっき処理、次いで、電解銅めっき処理を行い、スルーホール28を形成した。次に、図4(a)~(c)に示すように、配線パターン26をエッチング工法により作製し、試験片を得た。
参考例3-4の厚さ0.5mmのシートを用いたこと以外は参考例3-9と同様に、試験片を作製した。
比較例3-1の厚さ0.5mmのシートを用いたこと以外は参考例3-9と同様に、試験片を作製した。
参考例3-2の厚さ0.5mmのシートを用いたこと以外は参考例3-9と同様に、試験片を作製した。
参考例3-5の厚さ0.5mmのシートを用いたこと以外は参考例3-9と同様に、試験片を作製した。
比較例3-2の厚さ0.5mmのシートを用いたこと以外は参考例3-9と同様に、試験片を作製した。
6枚の試験片の電極に50Vの直流電圧をかけて、130℃85%の雰囲気下で放置試験を行なった。試験槽内で絶縁抵抗を測定し、試験開始から1時間後の絶縁抵抗値から、その100分の1になった時間を記録した。100時間を過ぎても絶縁抵抗値が下がらないものは、そこで終了とした。
[セルロースファイバー分散液の作製]
針葉樹クラフトパルプ(NBKP)を高圧ホモジナイザーで機械的に処理し、得られた数平均繊維径3μmのセルロースファイバーを水に添加して十分に撹拌し、セルロースファイバー10質量%の水懸濁液を作製した。これを脱水濾過し、濾物重量の10倍量のカルビトールアセテートを加え、30分間攪拌した後に濾過した。この置換操作を3回繰返して、濾物重量の10倍量のカルビトールアセテートを加え、10質量%のセルロースファイバー分散液を作製した。
下記表31および表32中の記載に従い、各成分を配合、攪拌して、3本ロールにて分散させて、各組成物を作製した。得られた組成物を、150mm×100mmの大きさで厚さ1.6mmのFR-4銅張り積層板(銅厚18μm)にスクリーン印刷法にて全面に印刷し、熱風循環式乾燥炉で140℃、30分間の条件で硬化させた。硬化後の膜厚は50μmであった。その後、過マンガン酸カリウム水溶液にて硬化物の表面を粗化し、無電解銅めっき、次いで電解銅めっきを全面につけて、評価基板を作製した。銅めっき部に、幅10mm、長さ100mmの部分の切込みをいれ、この一端を剥がしてつかみ具で掴み、室温中にて、50mm/分の速度で垂直方向に35mmを引き剥がした時の荷重(ピール強度)を測定した。
*4-2)熱硬化性化合物2:エピコート807 三菱化学(株)製
*4-3)硬化触媒1:2MZ-A 四国化成工業(株)製
*4-4)着色剤:フタロシアニンブルー
*4-5)有機溶剤:カルビトールアセテート
*4-7)熱硬化性化合物4:デナコールEX-830 ナガセケムテックス(株)製
*4-8)硬化触媒2:トリフェニルホスフィン
*4-13)光硬化性化合物2:トリメチロールプロパントリアクリレート
*4-14)光硬化性化合物3:カヤマーPM2 日本化薬(株)製
*4-15)光硬化性化合物4:ライトエステルHO 共栄社化学(株)製
*4-16)光重合開始剤1:2-エチルアントラキノン
*4-18)硬化触媒4:ジシアンジアミド
*4-19)光重合開始剤2:イルガキュア907 BASF社製
*4-20)光硬化性化合物5:ジペンタエリスリトルテトラアクリレート
*4-21)熱硬化性化合物5:TEPIC-H 日産化学(株)製
[カルボン酸塩を有するセルロースナノファイバー分散液の製造]
(製造例1)
針葉樹晒クラフトパルプ(王子製紙(株)製、水分50質量%、カナダ標準濾水度(CSF)550ml、主に数平均繊維径1000nm超の絶乾状態)5gを、2,2,6,6-テトラメチルピペリジン-N-オキシル(TEMPO)79mg(0.5mmol)と臭化ナトリウム515mg(5mmol)とを溶解した水溶液500mlに加え、パルプが均一分散するまで撹拌した。ここに、有効塩素5%の次亜塩素酸ナトリウム水溶液18mlを添加し、0.5N塩酸水溶液でpHを10に調整し、酸化反応を開始した。反応中は系内pHは低下するが、0.5N水酸化ナトリウム水溶液を逐次添加し、pHを10に調整した。2時間反応の後、ガラスフィルターで濾過し、濾物を十分に水洗して反応物を得た。
2,2,6,6-テトラメチルピペリジン-N-オキシル(TEMPO)79mg(0.5mmol)に代えて4-ジメチルアミノ-2,2,6,6-テトラメチルピペリジン-N-オキシル(4-ジメチルアミノ-TEMPO)100mg(0.5mmol)を用いた以外は、製造例1と同様にして、10質量%のカルボン酸塩を有するセルロースナノファイバー分散液2を作製した。なお、水分散液のカルボキシル基の量は1.30mmol/gであり、カルボン酸塩を有するセルロースナノファイバーの数平均繊維径は12nmであった。
2,2,6,6-テトラメチルピペリジン-N-オキシル(TEMPO)79mg(0.5mmol)に代えて4-カルボキシ-2,2,6,6-テトラメチルピペリジン-N-オキシル(4-カルボキシ-TEMPO)101mg(0.5mmol)を用いた以外は、製造例1と同様にして、10質量%のカルボン酸塩を有するセルロースナノファイバー分散液3を作製した。なお、水分散液のカルボキシル基の量は1.16mmol/gであり、カルボン酸塩を有するセルロースナノファイバーの数平均繊維径は10nmであった。
(製造例4)
ユーカリを製材した板を、カッターミルを用いて粉砕し、0.2mm角程度の木粉を作製した。次に、この木粉を、亜硫酸ナトリウムや水酸化ナトリウム等の水溶液中で高温高圧処理し、リグニンを除去した。50倍の蒸留水を加えて攪拌し、ディスクミルを用いた機械的粉砕を15回施した後、10質量%となるように蒸留水を加え、撹拌し、数平均繊維径80nmのセルロースナノファイバーを得た。これを脱水濾過し、濾物重量の10倍量のカルビトールアセテートを加え、30分間攪拌した後に濾過した。この置換操作を3回繰返して、濾物重量の10倍量のカルビトールアセテートを加え、10質量%のセルロースナノファイバー分散液1を作製した。
*5-2)熱硬化性化合物2:エピコート807 三菱化学(株)製
*5-3)硬化触媒1:2MZ-A 四国化成工業(株)製
*5-4)着色剤:フタロシアニンブルー
*5-5)有機溶剤:カルビトールアセテート
*5-7)熱硬化性化合物4:デナコールEX-830 ナガセケムテックス(株)製
*5-8)硬化触媒2:トリフェニルホスフィン
*5-11)光硬化性化合物2:トリメチロールプロパントリアクリレート
*5-12)光硬化性化合物3:カヤマーPM2 日本化薬(株)製
*5-13)光硬化性化合物4:ライトエステルHO 共栄社化学(株)製
*5-14)光重合開始剤1:2-エチルアントラキノン
*5-16)硬化触媒4:ジシアンジアミド
*5-17)光重合開始剤2:イルガキュア907 BASF製
*5-18)光硬化性化合物5:ジペンタエリスリトールテトラアクリレート
*5-19)熱硬化性化合物5:TEPIC-H 日産化学(株)製
上記表49の記載に従って、各成分を配合、攪拌して、3本ロールにて分散させて、各組成物を作製した。次に、この組成物を、厚さ18μmの銅箔に、スクリーン印刷法にて全面に印刷し、熱風循環式乾燥炉で140℃、30分間の条件で硬化させた。その後、銅箔を除去し、厚さ50μmの評価用シートを作製した。
JIS K7127に準拠し、上記評価用シートを所定の大きさに裁断して試験片を作製した。この試験片を、引張試験機((株)島津製作所製AGS-G)を用い、引っ張り速度10mm/分にて破断強度[MPa]、破断伸度[%]を測定した後、下記評価基準に基づき評価した。その結果を、下記の表56~表59に示す。破断強度および破断伸度の評価基準において、ともに○の場合、試験片の硬化物は高い靭性を有しており、耐クラック性に優れていることがわかる。
○:75MPa以上
△:50MPa以上75MPa未満
×:50MPa未満
(破断伸度の評価基準)
○:6%以上
△:4%以上6%未満
×:4%未満
上記破断強度および破断伸度評価シートの作製において、銅箔の代わりに1.6mmの厚さのFR-4銅張り積層板(銅厚18μm)を用い、膜厚20μmの硬化物を得た以外は同様の工程を経て、銅張り積層板上に硬化物が形成された評価用基板を作製した。
上記評価用基板を、-65℃で30分間、150℃で30分間を1サイクルとして、1000サイクルの温度履歴を与え、その後の評価用基板のクラックおよび剥離の程度を、光学顕微鏡((株)キーエンス製VHX-2000)により観察し、下記評価基準に基づき評価した。その結果を、下記の表56~表59に示す。
(評価基準)
○:クラック発生がない
△:クラック発生がある
×:クラック発生が著しい
[リグノセルロースナノファイバー分散液の製造]
(製造例1)
ユーカリを製材した板を、カッターミルを用いて粉砕し、0.2mm角程度の木粉を作製した。次に、この木粉に、その質量の50倍の蒸留水を加えて攪拌し、ディスクミルを用いた機械的粉砕を15回施した後、10質量%となるように蒸留水を加え、撹拌し、数平均繊維径80nmのセルロースナノファイバーを得た。これを脱水濾過し、濾物重量の10倍量のカルビトールアセテートを加え、30分間攪拌した後に濾過した。この置換操作を3回繰返して、濾物重量の10倍量のカルビトールアセテートを加え、10質量%のリグノセルロースナノファイバー分散液1を作製した。
杉を製材した板を、カッターミルを用いて粉砕し、0.2mm角程度の木粉を作製した。次に、この木粉に、その質量の50倍の蒸留水を加えて攪拌し、ディスクミルを用いた機械的粉砕を15回施した後、10質量%となるように蒸留水を加え、撹拌し、数平均繊維径80nmのセルロースナノファイバーを得た。これを脱水濾過し、濾物重量の10倍量のカルビトールアセテートを加え、30分間攪拌した後に濾過した。この置換操作を3回繰返して、濾物重量の10倍量のカルビトールアセテートを加え、10質量%のリグノセルロースナノファイバー分散液2を作製した。
(製造例3)
ユーカリを製材した板を、カッターミルを用いて粉砕し、0.2mm角程度の木粉を作製した。次に、この木粉を、亜硫酸ナトリウムや水酸化ナトリウム等の水溶液中で高温高圧処理し、リグニンを除去した。これに50倍の蒸留水を加えて攪拌し、ディスクミルを用いた機械的粉砕を15回施した後、10質量%となるように蒸留水を加え、撹拌し、数平均繊維径80nmのセルロースナノファイバーを得た。これを脱水濾過し、濾物重量の10倍量のカルビトールアセテートを加え、30分間攪拌した後に濾過した。この置換操作を3回繰返して、濾物重量の10倍量のカルビトールアセテートを加え、10質量%のセルロースナノファイバー分散液1を作製した。
下記の表60、表61、表64~表68中の記載に従って、各成分を配合、攪拌して、3本ロールにて分散させて、各組成物を作製した。なお、下記の表中の数字は、すべて質量部を示す。
*6-2)熱硬化性化合物2:エピコート807 三菱化学(株)製
*6-3)硬化触媒1:2MZ-A 四国化成工業(株)製
*6-4)顔料:フタロシアニンブルー
*6-5)有機溶剤:カルビトールアセテート
*6-7)熱硬化性化合物4:デナコールEX-830 ナガセケムテックス(株)製
*6-8)硬化触媒2:トリフェニルホスフィン
*6-13)光硬化性化合物2:トリメチロールプロパントリアクリレート
*6-14)光硬化性化合物3:カヤマーPM2 日本化薬(株)製
*6-15)光硬化性化合物4:ライトエステルHO 共栄社化学(株)製
*6-16)光重合開始剤1:2-エチルアントラキノン
*6-18)硬化触媒4:ジシアンジアミド
*6-19)光重合開始剤2:イルガキュア907(BASF社製)
*6-20)光硬化性化合物5:ジペンタエリスリトールテトラアクリレート
*6-21)熱硬化性化合物5:TEPIC-H(日産化学(株)製)
(試験基板の作製)
100mm×150mmの大きさで1.6mmの厚さのFR-4銅張り積層板(銅厚9μm)を用いて、エッチング工法によりIPC規格Bパターンのくし型電極のパターンを作製した。
耐電圧試験として、各6枚の試験片に昇圧速度毎秒500Vで直流電圧をかけて、破壊する電圧を測定した。6枚の平均が4.5kV以上の場合を○、4.5kV未満の場合を×と評価した。結果は、実施例6-1~実施例6-6のものは全て○であり、実施例6-7、比較例6-1のものは全て×であった。
また、絶縁信頼性試験として、各6枚の試験片に50Vの直流電圧をかけて、130℃、85%RHの雰囲気下で放置試験を行い、ショートするまでの時間を計測した。6枚の平均が200時間以上の場合を○、200時間未満の場合を×と評価した。結果は、実施例6-1~実施例6-6のものは全て○であり、実施例6-7、比較例6-1のものは全て×であった。
耐電圧試験として、各6枚の試験片に昇圧速度毎秒500Vで直流電圧をかけて、破壊する電圧を測定した。6枚の平均が5.5kV以上の場合を○、5.5kV未満の場合を×と評価した。結果は、実施例6-8~実施例6-13のものは全て○、実施例6-14、比較例6-2のものは全て×であった。
また、絶縁信頼性試験として、各6枚の試験片に50Vの直流電圧をかけて、130℃、85%RHの雰囲気下で放置試験を行い、ショートするまでの時間を計測した。6枚の平均が300時間以上の場合を○、300時間未満の場合を×と評価した。結果は、実施例6-8~実施例6-13のものは全て○であり、実施例6-14、比較例6-2のものは全て×であった。
耐電圧試験として、各6枚の試験片に昇圧速度毎秒500Vで直流電圧をかけて、破壊する電圧を測定した。6枚の平均が3.5kV以上の場合を○、3.5kV未満の場合を×と評価した。結果は、参考例6-1~参考例6-12のものは全て○であり、比較例6-3~比較例6-6のものは全て×であった。
また、絶縁信頼性試験として、各6枚の試験片に50Vの直流電圧をかけて、130℃、85%RHの雰囲気下で放置試験を行い、ショートするまでの時間を計測した。6枚の平均が250時間以上の場合を○、250時間未満の場合を×と評価した。結果は、参考例6-1~参考例6-12のものは全て○であり、比較例6-3~比較例6-6のものは全て×であった。
耐電圧試験として、各6枚の試験片に昇圧速度毎秒500Vで直流電圧をかけて、破壊する電圧を測定した。6枚の平均が5.5kV以上の場合を○、5.5kV未満の場合を×と評価した。結果は、参考例6-13~参考例6-18のものは全て○であり、比較例6-7、6-8のものは全て×であった。
また、絶縁信頼性試験として、各6枚の試験片に50Vの直流電圧をかけて、130℃、85%RHの雰囲気下で放置試験を行い、ショートするまでの時間を計測した。6枚の平均が250時間以上の場合を○、250時間未満の場合を×と評価した。結果は、参考例6-13~参考例6-18のものは全て○であり、比較例6-7、6-8のものは全て×であった。
耐電圧試験として、各6枚の試験片に昇圧速度毎秒500Vで直流電圧をかけて、破壊する電圧を測定した。6枚の平均が3.5kV以上の場合を○、3.5kV未満の場合を×と評価した。結果は、実施例6-15~実施例6-20のものは全て○であり、実施例6-21、比較例6-9のものは全て×であった。
また、絶縁信頼性試験として、各6枚の試験片に50Vの直流電圧をかけて、130℃、85%RHの雰囲気下で放置試験を行い、ショートするまでの時間を計測した。6枚の平均が100時間以上の場合を○、100時間未満の場合を×と評価した。結果は、実施例6-15~実施例6-20のものは全て○であり、実施例6-21、比較例6-9のものは全て×であった。
耐電圧試験として、各6枚の試験片に昇圧速度毎秒500Vで直流電圧をかけて、破壊する電圧を測定した。6枚の平均が4.5kV以上の場合を○、4.5kV未満の場合を×と評価した。結果は、実施例6-22~実施例6-34、実施例36~実施例41のものは全て○であり、実施例35、実施例42、比較例6-10~比較例6-12のものは全て×であった。
また、絶縁信頼性試験として、各6枚の試験片に50Vの直流電圧をかけて、130℃、85%RHの雰囲気下で放置試験を行い、ショートするまでの時間を計測した。6枚の平均が200時間以上の場合を○、200時間未満の場合を×と評価した。結果は、実施例6-22~実施例6-34、実施例36~実施例41のものは全て○であり、実施例35、実施例42、比較例6-10~比較例6-12のものは全て×であった。
実施例6-1~実施例6-7、比較例6-1の組成物を、100mm×150mmの大きさで1.6mmの厚さのFR-4銅張り積層板(銅厚9μm)に、スクリーン印刷法にて全面に印刷し、熱風循環式乾燥炉で140℃、30分間の条件で硬化させた。次に、無電解銅めっきをつけて、次いで、電解銅めっきをつけた。その後、エッチング工法により、IPC規格Bパターンのくし型電極のパターンをもつ試験片を作製した。
耐電圧試験として、各6枚の試験片に昇圧速度毎秒500Vで直流電圧をかけて、破壊する電圧を測定した。6枚の平均が5.5kV以上の場合を○、5.5kV未満の場合を×と評価した。結果は、実施例6-1~実施例6-6のものは全て○であり、実施例6-7、比較例6-1のものは全て×であった。
また、絶縁信頼性試験として、各6枚の試験片に50Vの直流電圧をかけて、130℃、85%RHの雰囲気下で放置試験を行い、ショートするまでの時間を計測した。6枚の平均が400時間以上の場合を○、400時間未満の場合を×と評価した。結果は、実施例6-1~実施例6-6のものは全て○であり、実施例6-7、比較例6-1のものは全て×であった。
耐電圧試験として、各6枚の試験片に昇圧速度毎秒500Vで直流電圧をかけて、破壊する電圧を測定した。6枚の平均が6.5kV以上の場合を○、6.5kV未満の場合を×と評価した。結果は、実施例6-8~実施例6-13のものは全て○であり、実施例6-14、比較例6-2のものは全て×であった。
また、絶縁信頼性試験として、各6枚の試験片に50Vの直流電圧をかけて、130℃、85%RHの雰囲気下で放置試験を行い、ショートするまでの時間を計測した。6枚の平均が500時間以上のものを○、500時間未満のものを×と評価した。結果は実施例6-8から実施例6-13のものは全て○であり、実施例6-14、比較例6-2のものは全て×であった。
耐電圧試験として、各6枚の試験片に昇圧速度毎秒500Vで直流電圧をかけて、破壊する電圧を測定した。6枚の平均が4.5kV以上の場合を○、4.5kV未満の場合を×と評価した。結果は、参考例6-1~参考例6-12のものは全て○であり、比較例6-3~比較例6-6のものは全て×であった。
また、絶縁信頼性試験として、各6枚の試験片に50Vの直流電圧をかけて、130℃、85%RHの雰囲気下で放置試験を行い、ショートするまでの時間を計測した。6枚の平均が400時間以上の場合を○、400時間未満の場合を×と評価した。結果は、参考例6-1~参考例6-12のものは全て○であり、比較例6-3~比較例6-6のものは全て×であった。
耐電圧試験として、各6枚の試験片に昇圧速度毎秒500Vで直流電圧をかけて、破壊する電圧を測定した。6枚の平均が6kV以上の場合を○、6kV未満の場合を×と評価した。結果は、参考例6-13~参考例6-18のものは全て○であり、比較例6-7、6-8のものは全て×であった。
また、絶縁信頼性試験として、各6枚の試験片に50Vの直流電圧をかけて、130℃、85%RHの雰囲気下で放置試験を行い、ショートするまでの時間を計測した。6枚の平均が400時間以上の場合を○、400時間未満の場合を×と評価した。結果は、参考例6-13~参考例6-18のものは全て○であり、比較例6-7、6-8のものは全て×であった。
耐電圧試験として、各6枚の試験片に昇圧速度毎秒500Vで直流電圧をかけて、破壊する電圧を測定した。6枚の平均が4.5kV以上の場合を○、4.5kV未満の場合を×と評価した。結果は、実施例6-15~実施例6-20のものは全て○であり、実施例6-21、比較例6-9のものは全て×であった。
また、絶縁信頼性試験として、各6枚の試験片に50Vの直流電圧をかけて、130℃、85%RHの雰囲気下で放置試験を行い、ショートするまでの時間を計測した。6枚の平均が250時間以上の場合を○、250時間未満の場合を×と評価した。結果は、実施例6-15~実施例6-20のものは全て○であり、実施例6-21、比較例6-9のものは全て×であった。
耐電圧試験として、各6枚の試験片に昇圧速度毎秒500Vで直流電圧をかけて、破壊する電圧を測定した。6枚の平均が5.5kV以上の場合を○、5.5kV未満の場合を×と評価した。結果は、実施例6-22~実施例6-34、実施例6-36~実施例6-41のものは全て○であり、実施例6-35、実施例6-42、比較例6-10~比較例6-12のものは全て×であった。
また、絶縁信頼性試験として、各6枚の試験片に50Vの直流電圧をかけて、130℃、85%RHの雰囲気下で放置試験を行い、ショートするまでの時間を計測した。6枚の平均が400時間以上の場合を○、400時間未満の場合を×と評価した。結果は、実施例6-22~実施例6-34、実施例6-36~実施例6-41のものは全て○であり、実施例6-35、実施例6-42、比較例6-10~比較例6-12のものは全て×であった。
(リグノセルロースナノファイバーシートの作製)
リグノセルロースナノファイバー分散液1およびリグノセルロースナノファイバー分散液2について、カルビトールアセテートにて0.2質量%分散液を作製し、ガラスフィルターで濾過して、100mm×150mmの大きさで厚み40μmのシートを作製した。
セルロースナノファイバー分散液1について、カルビトールアセテートにて0.2質量%分散液を作製し、ガラスフィルターで濾過して、100mm×150mmの大きさで厚み40μmのシートを作製した。
耐電圧試験として、各6枚の試験片に昇圧速度毎秒500Vで直流電圧をかけて、破壊する電圧を測定した。6枚の平均が5.5kV以上の場合を○、5.5kV未満の場合を×と評価した。結果は、実施例6-43、6-44のものは全て○であり、実施例6-45、比較例6-13のものは全て×であった。
また、絶縁信頼性試験として、各6枚の試験片に50Vの直流電圧をかけて、130℃、85%RHの雰囲気下で放置試験を行い、ショートするまでの時間を計測した。6枚の平均が400時間以上の場合を○、400時間未満の場合を×と評価した。結果は、実施例6-43、6-44のものは全て○であり、実施例6-45、比較例6-13のものは全て×であった。
耐電圧試験として、各6枚の試験片に昇圧速度毎秒500Vで直流電圧をかけて、破壊する電圧を測定した。6枚の平均が6.5kV以上の場合を○、6.5kV未満の場合を×と評価した。結果は、実施例6-46、6-47のものは全て○であり、実施例6-48、比較例6-14のものは全て×であった。
また、絶縁信頼性試験として、各6枚の試験片に50Vの直流電圧をかけて、130℃、85%RHの雰囲気下で放置試験を行い、ショートするまでの時間を計測した。6枚の平均が500時間以上の場合を○、500時間未満の場合を×と評価した。結果は、実施例6-46、6-47のものは全て○であり、実施例6-48、比較例6-14のものは全て×であった。
耐電圧試験として、各6枚の試験片に昇圧速度毎秒500Vで直流電圧をかけて、破壊する電圧を測定した。6枚の平均が6kV以上の場合を○、6kV未満の場合を×と評価した。結果は、参考例6-19、6-20のものは全て○であり、比較例6-15、6-16のものは全て×であった。
また、絶縁信頼性試験として、各6枚の試験片に50Vの直流電圧をかけて、130℃、85%RHの雰囲気下で放置試験を行い、ショートするまでの時間を計測した。6枚の平均が400時間以上の場合を○、400時間未満の場合を×と評価した。結果は、参考例6-19、6-20のものは全て○であり、比較例6-15、6-16のものは全て×であった。
耐電圧試験として、各6枚の試験片に昇圧速度毎秒500Vで直流電圧をかけて、破壊する電圧を測定した。6枚の平均が4.5kV以上の場合を○、4.5kV未満の場合を×と評価した。結果は、参考例6-1~参考例6-12のものは全て○であり、比較例6-3~比較例6-6のものは全て×であった。
また、絶縁信頼性試験として、各6枚の試験片に50Vの直流電圧をかけて、130℃、85%RHの雰囲気下で放置試験を行い、ショートするまでの時間を計測した。6枚の平均が400時間以上の場合を○、400時間未満の場合を×と評価した。結果は、参考例6-1~参考例6-12のものは全て○であり、比較例6-3~比較例6-6のものは全て×であった。
2 コア基板
1a,4 コネクション部
5 スルーホール
6,9 層間絶縁層
7,10 ビア
12 ソルダーレジスト層
21 銅張り積層板(試験基板)
21a 導体層
21b 絶縁層
22 絶縁樹脂層
23 レーザービア
24 めっき層
25 エッチングレジストパターン
26 配線パターン
27 貫通穴
28 スルーホール
Claims (11)
- 硬化性樹脂と、数平均繊維径3nm~1000nmのセルロースナノファイバーと、を含むことを特徴とするソルダーレジスト組成物。
- 前記硬化性樹脂が、熱硬化性樹脂および光硬化性樹脂のうちから選択される請求項1記載のソルダーレジスト組成物。
- 前記硬化性樹脂がカルボキシル基含有樹脂を含む請求項2記載のソルダーレジスト組成物。
- 層状珪酸塩を含む請求項1記載のソルダーレジスト組成物。
- シリコーン化合物およびフッ素化合物のうちのいずれか一方または双方を含む請求項1記載のソルダーレジスト組成物。
- 前記セルロースナノファイバーの数平均繊維径が3nm以上1000nm未満であって、さらに、数平均繊維径1μm以上のセルロースファイバーを含む請求項1記載のソルダーレジスト組成物。
- 前記セルロースナノファイバーが、その構造中にカルボン酸塩を有する請求項1記載のソルダーレジスト組成物。
- 前記セルロースナノファイバーが、リグノセルロースから製造された請求項1記載のソルダーレジスト組成物。
- 請求項1~8のうちいずれか一項記載のソルダーレジスト組成物を、キャリアフィルム上に塗布、乾燥させて得られることを特徴とするドライフィルム。
- 請求項1~8のうちいずれか一項記載のソルダーレジスト組成物を、基材上に塗布、乾燥させて得られる乾燥塗膜、または、前記ソルダーレジスト組成物を、キャリアフィルム上に塗布、乾燥させて得られるドライフィルムが基材にラミネートされてなる塗膜を、硬化させて得られることを特徴とする硬化物。
- 請求項10記載の硬化物を有することを特徴とするプリント配線板。
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WO2023190456A1 (ja) * | 2022-03-31 | 2023-10-05 | 太陽ホールディングス株式会社 | 硬化物、感光性樹脂組成物、ドライフィルムおよびプリント配線板 |
EP4299296A1 (en) * | 2022-06-27 | 2024-01-03 | PaperShell AB | Alternative for fr-4 material |
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KR20160005028A (ko) | 2016-01-13 |
CN105075409A (zh) | 2015-11-18 |
TWI637991B (zh) | 2018-10-11 |
CN105075409B (zh) | 2018-07-03 |
KR102218425B1 (ko) | 2021-02-22 |
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