WO2014115629A1 - 受容層形成用組成物、それを用いて得られる受容基材、印刷物、導電性パターン及び電気回路 - Google Patents
受容層形成用組成物、それを用いて得られる受容基材、印刷物、導電性パターン及び電気回路 Download PDFInfo
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- WO2014115629A1 WO2014115629A1 PCT/JP2014/050646 JP2014050646W WO2014115629A1 WO 2014115629 A1 WO2014115629 A1 WO 2014115629A1 JP 2014050646 W JP2014050646 W JP 2014050646W WO 2014115629 A1 WO2014115629 A1 WO 2014115629A1
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- receiving layer
- forming
- composition
- receiving
- conductive
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
- B41M5/52—Macromolecular coatings
- B41M5/5263—Macromolecular coatings characterised by the use of polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- 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
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
- B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
- B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
- B41J2/01—Ink jet
-
- 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
- C09D11/00—Inks
- C09D11/52—Electrically conductive inks
-
- 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
- H05K1/09—Use of materials for the conductive, e.g. metallic pattern
- H05K1/092—Dispersed materials, e.g. conductive pastes or inks
-
- 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
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/12—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns
- H05K3/1208—Pretreatment of the circuit board, e.g. modifying wetting properties; Patterning by using affinity patterns
-
- 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
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/12—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns
- H05K3/1241—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns by ink-jet printing or drawing by dispensing
- H05K3/125—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns by ink-jet printing or drawing by dispensing by ink-jet printing
-
- 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
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material
- H05K3/181—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating
- H05K3/182—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating characterised by the patterning method
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
- B32B2307/202—Conductive
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/402—Coloured
- B32B2307/4026—Coloured within the layer by addition of a colorant, e.g. pigments, dyes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/75—Printability
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/08—PCBs, i.e. printed circuit boards
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
-
- 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
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/07—Treatments involving liquids, e.g. plating, rinsing
- H05K2203/0703—Plating
- H05K2203/0709—Catalytic ink or adhesive for electroless plating
Definitions
- the present invention relates to a composition for forming a receiving layer capable of receiving a fluid such as ink, a receiving substrate provided with a receiving layer formed using the composition, and a printed matter such as a conductive pattern.
- the pigment ink having the high color developability even when the pigment ink having the high color developability is used, there may be a problem that the pigment peels off from the support over time.
- various materials are used as a support on which the ink receiving layer is provided.
- adhesion to a plastic film such as polyethylene terephthalate is achieved.
- the receptor layer may be peeled off with time.
- a conductive ink containing a conductive material such as silver is printed on the support surface by an ink jet printing method, a screen printing method, or the like, and then dried. And the method of heating and light irradiation as needed is mentioned.
- the conductive ink is not easily adhered to the surface of the support, and thus easily peels off. In some cases, disconnection may occur.
- the support made of polyimide resin or polyethylene terephthalate resin is flexible, so that it is possible to produce a flexible device that can be bent.
- the support made of polyimide resin or the like is particularly in close contact with ink or resin. Since it is difficult to peel off, it is easy to peel off, which may cause disconnection of the finally obtained electronic circuit or the like, thereby preventing current conduction.
- a method of producing a conductive pattern by drawing a pattern by a predetermined method using a conductive ink on an ink receiving substrate provided with a latex layer is known. It is known that a urethane resin can be used as the latex layer (see, for example, Patent Document 1).
- the adhesion of the ink receiving layer comprising the latex layer constituting the conductive pattern was not one step beyond the level that can be used for applications such as electrical circuits.
- a printed matter printed with the conductive ink is generally used for the purpose of bringing the conductive substances contained in the conductive ink into contact with each other to impart conductivity. In many cases, it is heated and baked at a temperature of °C or higher.
- the ink receiving layer such as the latex layer described in the literature 1 is easily deteriorated due to the influence of heat received in the baking process, the adhesion of the interface between the ink receiving layer and the support is particularly high. It is easy to cause a drop, and even if a very slight force is applied, it may be easily peeled off.
- the latex layer that is the ink receiving layer is likely to be excessively swollen and deformed during the baking process, it may cause disconnection of the electric circuit or poor conduction.
- the latex layer often does not have sufficient adhesion to the support before heating in the baking step, the support and the ink receiving layer are not subjected to the baking step. And may cause partial peeling.
- the plating process is performed by using, for example.
- the plating agent used for the plating treatment and the agent used in the cleaning step are usually strongly alkaline and strongly acidic, and thus easily cause peeling from the support such as the receiving layer.
- the conductive pattern may be disconnected.
- the conductive pattern is required to have a level of durability that does not cause peeling of the conductive ink-receiving layer from the support even when it is repeatedly immersed in the drug or the like for a long time. ing.
- the problem to be solved by the present invention is a composition for forming a receiving layer capable of supporting a fluid such as ink and forming a receiving layer capable of providing excellent adhesion between various supports and a conductive layer. Is to provide.
- the second problem to be solved by the present invention is that it is possible to carry a fluid such as a conductive ink, and even when a chemical such as a plating chemical or various organic solvents adheres, the support for the receiving layer It is an object of the present invention to provide a composition for forming a receiving layer capable of forming a printed matter such as a conductive pattern having a level of durability that does not cause peeling from the surface.
- the composition of the present invention can solve the problems of the present invention if it is a composition for forming a receiving layer containing a specific amount of blocked isocyanate (A).
- the present invention relates to a composition for forming a receiving layer, characterized in that the blocked isocyanate (A) is contained in an amount of 50 to 100% by weight based on the solid content of the composition for forming a receiving layer.
- the receiving layer forming composition of the present invention since it has excellent adhesion to various supports, it can be used, for example, in a recording medium used for manufacturing advertisements, signboards, signs, etc. that can be installed indoors and outdoors. can do.
- a receiving layer having excellent adhesion between the receiving layer and the support can be formed, and durability at a level that does not cause peeling of the receiving layer in a plating process or the like.
- a conductive ink containing a conductive material such as silver, an organic solar cell or an electronic book terminal, an organic EL, an organic transistor, a flexible printed circuit board,
- the composition for forming a receiving layer of the present invention is characterized in that the blocked isocyanate (A) is contained in an amount of 50% by mass to 100% by mass based on the solid content of the composition for forming the receiving layer.
- the composition for forming a receiving layer exclusively absorbs the solvent in the fluid when the fluid containing the conductive material or the pigment contacts, and forms the receiving layer carrying the conductive material or the pigment. It can be used for.
- the blocked isocyanate (A) forms a uretdione bond by self-reacting between isocyanate groups, or forms a receptor layer by forming a bond between an isocyanate group and a functional group of another component.
- the bond may be formed before the fluid is applied, or the bond is not formed before the fluid is applied, and is heated after the fluid is applied.
- the bond may be formed.
- blocked isocyanate (A) contained in the receiving layer forming composition those having a functional group [a] formed by blocking an isocyanate group with a blocking agent can be used.
- the blocked isocyanate (A) may be one having the functional group [a] in the range of 350 g / mol to 600 g / mol per 1 mol of the blocked isocyanate (A). It is preferable for imparting even better adhesion.
- the functional group [a] preferably has 1 to 10 functional groups [A] in one molecule of the blocked isocyanate (A), and using 2 to 5 functional groups further improves the adhesion. More preferable.
- the blocked isocyanate (A) preferably has a number average molecular weight in the range of 1,000 to 5,000 in order to further improve the adhesion. More preferably, those having a number average molecular weight in the range of 1,000.
- the blocked isocyanate (A) it is preferable to use one having an aromatic structure from the viewpoint of imparting further excellent adhesion.
- the aromatic structure include a phenyl group and a naphthyl group.
- the blocked isocyanate (A) may have a urethane bond or a urea bond, but the presence ratio of the urethane bond and the urea bond is 500 g / mol to 1 per mole of the blocked isocyanate (A). , 500 g / mol is preferable because the adhesion can be further improved.
- the blocked isocyanate (A) can be produced by reacting a part or all of the isocyanate groups of the isocyanate compound (a-1) with a blocking agent.
- the isocyanate compound (a-1) that can be used for the production of the blocked isocyanate (A) those having an isocyanate group can be used, for example, 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate.
- isocyanate compound (a-1) a compound obtained by reacting the polyisocyanate compound (a-1-1) with a compound having a hydroxyl group or an amino group can be used.
- the compound having a hydroxyl group it is preferable to use a compound having a hydrophilic group and a hydroxyl group in order to give better adhesiveness to the blocked isocyanate (A).
- the blocked isocyanate (A) is used in combination with the aqueous medium (B)
- the blocked isocyanate (A) has good water dispersion stability by using a compound having a hydrophilic group and a hydroxyl group. Since it can provide, it is preferable.
- Examples of the compound having a hydrophilic group and a hydroxyl group include a polyol having a carboxyl group such as 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 2,2-dimethylolvaleric acid, and the like; Polyols having a sulfonic acid group such as acid, sulfoterephthalic acid, 4-sulfophthalic acid, and 5- (4-sulfophenoxy) isophthalic acid can be used.
- Examples of the compound having a hydrophilic group and a hydroxyl group include compounds having a nonionic group such as polyethylene glycol, polyethylene-polypropylene copolymer, polyethylene glycol monomethyl ether, polyethylene glycol monoethyl ether, polyethylene glycol monopropyl ether, polyethylene glycol monobutyl ether. Etc. can be used.
- a compound having a hydrophilic group and an amino group can be used.
- 2-aminopropionic acid, 2-aminoethylsulfonic acid, 4-aminobenzenesulfonic acid, 2, 6-diaminohexanoic acid, 2,5-diaminovaleric acid and the like can be used.
- the isocyanate compound (a-1) it is preferable to use a polyisocyanate compound having an aromatic structure in order to further improve the adhesion by introducing the aromatic structure into the block polyisocyanate (A). .
- a polyisocyanate compound having an aromatic structure in order to further improve the adhesion by introducing the aromatic structure into the block polyisocyanate (A).
- 4,4'-diphenylmethane diisocyanate, tolylene diisocyanate, isocyanurate of 4,4'-diphenylmethane diisocyanate, and isocyanurate of tolylene diisocyanate are more preferably used.
- Examples of the blocking agent that can be used in the production of the blocked isocyanate (A) include phenol compounds such as phenol and cresol; lactams such as ⁇ -caprolactam, ⁇ -valerolactam, and ⁇ -butyrolactam; formamide oxime, acetoaldoxime, acetone Oximes such as oxime, methyl ethyl ketoxime, methyl isobutyl ketoxime, cyclohexanone oxime, 2-hydroxypyridine, butyl cellosolve, propylene glycol monomethyl ether, benzyl alcohol, methanol, ethanol, n-butanol, isobutanol, dimethyl malonate, malonic acid Diethyl, methyl acetoacetate, ethyl acetoacetate, acetylacetone, butyl mercaptan, dodecyl mercaptan, acetanilide, acetic acid Imide, succinimide
- a blocking agent that can be dissociated by heating to 70 ° C. to 200 ° C., more preferably 110 ° C. to 180 ° C. to generate an isocyanate group, and the phenol compound, lactam, and oxime can be used. More preferably it is used.
- the blocked isocyanate (A) may be produced by mixing and reacting the isocyanate compound (a-1) produced in advance with the blocking agent, and for producing the isocyanate compound (a-1). You may manufacture by mixing the said blocking agent with the raw material to be used, and making it react.
- the blocked isocyanate (A) used in the present invention has an isocyanate group at the terminal by reacting the polyisocyanate compound (a-1-1) with a compound having a hydroxyl group or an amino group.
- the isocyanate compound (a-1) can be produced, and then the isocyanate compound (a-1) and the blocking agent can be mixed and reacted.
- the blocked isocyanate (A) obtained by the above method is preferably contained in the range of 50% by mass to 100% by mass with respect to the total amount of the solid content of the composition for forming a receiving layer of the present invention, and further 70% by mass.
- the composition for forming a receiving layer of the present invention may contain a solvent capable of dissolving or dispersing the solid content such as the blocked isocyanate (A).
- an aqueous medium (B), an organic solvent, or the like can be used.
- Examples of the aqueous medium (B) include water, organic solvents miscible with water, and mixtures thereof.
- the organic solvent miscible with water include alcohols such as methanol, n- and isopropanol; ketones such as acetone and methyl ethyl ketone; polyalkylene glycols such as ethylene glycol, diethylene glycol and propylene glycol; alkyl ethers of polyalkylene glycol; N— And lactams such as methyl-2-pyrrolidone.
- only water may be used, a mixture of water and an organic solvent miscible with water may be used, or only an organic solvent miscible with water may be used. From the viewpoint of safety and load on the environment, water alone or a mixture of water and an organic solvent miscible with water is preferable, and only water is particularly preferable.
- organic solvent for example, toluene, ethyl acetate, methyl ethyl ketone, or the like can be used.
- a solvent containing the aqueous medium (B) as the solvent for the blocked isocyanate (A), and water may be used alone as the aqueous medium (B), or water and water may be mixed. A mixture with an organic solvent may be used.
- the aqueous medium (B) is preferably contained in an amount of 60 to 99% by mass, and preferably 70 to 99% by mass, based on the total amount of the composition for forming a receiving layer of the present invention. Accordingly, the solid content of the receptor layer forming composition of the present invention is preferably in the range of 1% by mass to 40% by mass with respect to the total amount of the receptor layer forming composition. % Is more preferable.
- a hydrophilic group is used as the blocked isocyanate (A), particularly for the purpose of imparting water dispersion stability and storage stability to the blocked isocyanate (A).
- examples thereof include a method of using a blocked isocyanate having a surfactant and a method of using a surfactant in combination.
- hydrophilic group for example, an anionic group, a cationic group, or a nonionic group can be used, and an anionic group is more preferably used.
- anionic group for example, a carboxyl group, a carboxylate group, a sulfonic acid group, a sulfonate group, and the like can be used. Among them, a part or all of the carboxyl group or sulfonic acid group is neutralized by a basic compound. It is preferable to use the carboxylate group or sulfonate group thus formed in order to impart excellent water dispersion stability.
- Examples of basic compounds that can be used to neutralize the anionic group include organic amines such as ammonia, triethylamine, pyridine, morpholine, alkanolamines such as monoethanolamine, metal bases including sodium, potassium, lithium, and calcium. Compounds. When forming a conductive pattern or the like, it is preferable to use the organic amine or alkanolamine because the metal salt compound may inhibit the conductivity.
- the carboxylate group or sulfonate group is used as the anionic group, they are preferably present in the range of 5 mmol / kg to 4,000 mmol / kg with respect to the whole blocked isocyanate (A), and 50 mmol / kg. It is more preferable that it is present in the range of ⁇ 2,000 mmol / kg in order to maintain good water dispersion stability of the blocked isocyanate (A).
- a tertiary amino group can be used, for example.
- the acid that can be used for neutralizing part or all of the tertiary amino group include organic acids such as acetic acid, propionic acid, lactic acid, and maleic acid, and organic acids such as sulfonic acid and methanesulfonic acid.
- nonionic group examples include polyoxyalkylene groups such as polyoxyethylene group, polyoxypropylene group, polyoxybutylene group, poly (oxyethylene-oxypropylene) group, and polyoxyethylene-polyoxypropylene group. Can be used. Among these, it is preferable to use a polyoxyalkylene group having an oxyethylene unit in order to further improve the hydrophilicity.
- the hydrophilic group is a compound having a hydrophilic group and a hydroxyl group such as 2,2-dimethylolpropionic acid as described above when the blocked isocyanate (A) is produced, and the isocyanate compound (a1-1). It can introduce
- Examples of the surfactant that can be used for the purpose of imparting water dispersion stability to the blocked isocyanate (A) include anionic surfactants, nonionic surfactants, and cationic surfactants. And zwitterionic surfactants.
- anionic surfactant examples include sulfates of higher alcohols and salts thereof, alkylbenzene sulfonates, polyoxyethylene alkylphenyl sulfonates, polyoxyethylene alkyl diphenyl ether sulfonates, and polyoxyethylene alkyl ethers.
- non-ionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl phenyl ether, and polyoxyethylene alkyl phenyl ether.
- Ethylene diphenyl ether, polyoxyethylene-polyoxypropylene block copolymer, acetylenic diol surfactant and the like can be used.
- cationic surfactant for example, an alkyl ammonium salt or the like can be used.
- alkyl (amido) betaine alkyldimethylamine oxide and the like can be used.
- surfactant in addition to the above-mentioned ones, fluorine surfactants, silicone surfactants and the like can be used.
- the receptor layer-forming composition of the present invention constitutes the solid content thereof, in addition to the blocked isocyanate (A), if necessary, a resin, a curing agent, a filler, a pH adjuster, a film formation aid. It may contain other compounds such as an agent, a leveling agent, a thickener, a water repellent, and an antifoaming agent.
- the resin is preferably used in order to further improve the printability and fine lineability when using a fluid such as aqueous pigment ink, conductive ink, or plating nucleating agent.
- the resin examples include vinyl resins such as acrylic resins, urethane resins, urethane-vinyl composite resins, polyester resins, imide resins, epoxy resins, polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl acetal, polyalkylene oxide, starch, methyl cellulose, and hydroxy cellulose. Further, cellulose derivatives such as hydroxypropylcellulose, hydroxypropylmethylcellulose, carboxymethylcellulose, polyethyleneimine, polyamide, various quaternary ammonium base-containing water-soluble resins, and modified products thereof can be used.
- vinyl resins such as acrylic resins, urethane resins, urethane-vinyl composite resins, polyester resins, imide resins, epoxy resins, polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl acetal, polyalkylene oxide, starch, methyl cellulose, and hydroxy cellulose.
- cellulose derivatives such as hydroxypropylcellulose,
- a compound having a functional group capable of reacting with an isocyanate group generated by dissociation of the blocking agent by heating or the like can be used.
- Relatively low molecular weight polyols such as hexamethylene glycol, saccharose, methylene glycol, glycerin, sorbitol, metal chelate compounds, polyamine compounds, aziridine compounds, metal salt compounds, etc.
- the other compounds various fillers such as inorganic particles can be used.
- the amount of the filler used is preferably as small as possible, and is 5% by mass or less based on the total amount of the composition for forming a receiving layer of the present invention. More preferred.
- the amount of the other compound used is preferably in the range of 0% by mass to 50% by mass, and in the range of 0% by mass to 30% by mass with respect to the solid content contained in the composition for forming the receiving layer. It is more preferable.
- the receiving layer that can be formed using the receiving layer forming composition is prepared by appropriately dissolving the block polyisocyanate (A) constituting the receiving layer or a cured product thereof with a solvent contained in a fluid such as ink. By absorbing the solvent, it is a swelling type that can accurately fix conductive substances such as metals and pigments contained in the fluid to the surface of the receiving layer, so that conductive patterns without bleeding etc. It is possible to obtain printed matter.
- the composition for forming a receiving layer of the present invention can form a transparent receiving layer as compared with a conventionally known porous type receiving layer.
- the receiving substrate of the present invention has a receiving layer formed by using the receiving layer forming composition on a part or all of the surfaces of various supports and on one or both sides of the support.
- the receptor layer is a layer that absorbs a solvent in the fluid when the fluid contacts the surface of the receptor layer and carries a conductive substance or pigment on the surface of the receptor layer.
- a pigment ink is used as the fluid, it is possible to form a highly clear printed matter without bleeding, and if a conductive ink is used as the fluid, a conductive pattern without bleeding.
- a plating nucleating agent is used as the fluid, a laminated body in which the plating nuclei are uniformly supported on the surface of the receiving layer can be formed.
- the receiving layer may be laminated on the support, but a part of the receiving layer may be impregnated in the support.
- the receiving substrate of the present invention is a method in which the composition for forming a receiving layer is applied to a part or all of one or both sides of a support, and the aqueous medium (B) contained in the coated surface is volatilized or supported.
- the body is a fiber substrate, it can be produced by a method of impregnating the support layer-forming composition into the support and volatilizing the aqueous medium (B).
- the support examples include fine paper, coated paper, polyimide resin, polyamideimide resin, polyamide resin, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, acrylonitrile-butadiene-styrene (ABS), poly (meth) acrylate, and the like.
- a support made of a metal such as a steel plate or copper can be used.
- a base material made of synthetic fibers such as polyester fiber, polyamide fiber, and aramid fiber, natural fibers such as cotton and hemp can be used as the support.
- the fibers may be processed in advance.
- a method of applying or impregnating the composition for forming a receiving layer on the support known and conventional methods can be used, for example, gravure method, coating method, screen method, roller method, rotary method, spray method. Etc. can be applied.
- the method for removing the solvent that may be contained in the composition after coating or impregnating the support layer-forming composition of the present invention on part or all of the surface of the support is not particularly limited.
- a method of drying using a dryer is common.
- the drying temperature may be set to a temperature that can volatilize the solvent and does not adversely affect the support.
- the adhesion amount of the composition for forming a receiving layer on the support is 3 g / m 2 with respect to the area of the support from the viewpoint of maintaining a very high level of color developability and maintaining good production efficiency. It is preferably in the range of ⁇ 60 g / m 2 , and 20 g / m 2 to 40 g / m 2 is particularly preferred in consideration of the absorbability of the solvent contained in the fluid and the production cost.
- the adhesion amount of the composition for forming a receiving layer on the support it is possible to further improve the color developability of the obtained printed matter.
- the texture of the printed matter tends to be slightly harder as the adhesion amount increases, it is preferable to adjust appropriately according to the use purpose of the printed matter.
- the receiving substrate of the present invention can form a printed image having excellent printability and water resistance without causing bleeding or cracking, it can be used for indoor and outdoor advertisements such as signboards, body advertisements, and banners. It can be used.
- the fluid that can be used for printing on the receiving substrate has a viscosity measured by a B-type viscometer at approximately 25 ° C. of 0.1 mPa ⁇ s to 500,000 mPa ⁇ s, preferably 0.5 mPa ⁇ s to 10, A liquid or viscous liquid having a viscosity of 000 mPa ⁇ s, in which a conductive substance, a pigment, or the like is dispersed in a solvent.
- the fluid include printing inks such as conductive inks and pigment inks, and plating nucleating agents that may be used when plating is performed.
- Examples of the fluid include an aqueous pigment ink in which a pigment is dispersed in an aqueous medium.
- aqueous medium only water may be used, or a mixed solution of water and a water-soluble solvent may be used.
- water-soluble solvent include alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, ethyl carbitol, ethyl cellosolve, and butyl cellosolve, and polar solvents such as N-methylpyrrolidone.
- pigments that can be dispersed or dissolved in the aqueous medium include, for example, quinacridone, anthraquinone, perylene, perinone, diketopyrrolopyrrole, isoindolinone, condensed azo, benzimidazolone, and monoazo.
- Organic pigments such as insoluble azo, naphthol, flavanthrone, anthrapyrimidine, quinophthalone, pyranthrone, pyrazolone, thioindigo, anthanthrone, dioxazine, phthalocyanine, indanthrone, nickel dioxin Metal complexes such as yellow and copper azomethine yellow, metal oxides such as titanium oxide, iron oxide and zinc oxide, metal salts such as barium sulfate and calcium carbonate, inorganic pigments such as carbon black and mica, metal fine powder such as aluminum and mica It is possible to use fine powder That.
- the pigment is preferably used in an amount of 0.5 to 15% by mass, more preferably 1 to 10% by mass, based on the total amount of the aqueous pigment ink.
- a solvent-based pigment ink in which a pigment or the like is dissolved or dispersed in a solvent composed of an organic solvent can also be used.
- organic solvent for example, alcohol, ether, ester, ketone and the like having a boiling point of 100 to 250 ° C., preferably having a boiling point of 120 to 220, are used from the viewpoint of preventing drying and clogging of the inkjet head. More preferred is one at ° C.
- ethylene glycol for example, ethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol and the like can be used.
- ethers include ethylene glycol mono (methyl, ethyl, butyl, phenyl, benzyl, ethylhexyl) ether, ethylene glycol di (methyl, ethyl, butyl) ether, diethylene glycol mono (methyl, ethyl, butyl) ether, diethylene glycol di ( Methyl, ethyl, butyl) ether, tetraethylene glycol mono (methyl, ethyl, butyl) ether, tetraethylene glycol di (methyl, ethyl, butyl) ether, propylene glycol mono (methyl, ethyl, butyl) ether, dipropylene glycol mono (Methyl, ethyl) ether, tripropylene glycol monomethyl ether and the like can be used.
- esters include ethylene glycol mono (methyl, ethyl, butyl) ether acetate, ethylene glycol di (methyl, ethyl, butyl) ether acetate, diethylene glycol mono (methyl, ethyl, butyl) ether acetate, diethylene glycol di (methyl, ethyl) , Butyl) ether acetate, propylene glycol mono (methyl, ethyl, butyl) ether acetate, dipropylene glycol mono (methyl, ethyl) ether acetate, tripropylene glycol monomethyl ether acetate, 2- (methoxy, ethoxy, butoxy) ethyl acetate, Examples include 2-ethylhexyl acetate, dimethyl phthalate, diethyl phthalate, and butyl lactate. Examples of ketones include cyclohexanone.
- diethylene glycol diethyl ether tetraethylene glycol monobutyl ether, tetraethylene glycol dimethyl ether, ethylene glycol monobutyl ether acetate, and propylene glycol monomethyl ether acetate are preferably used.
- the same pigments exemplified as those usable in the aqueous pigment ink can be used.
- the receiving substrate of the present invention can be suitably used particularly when printing is performed using a solvent-based pigment ink among the pigment inks composed of the water-based pigment ink and the solvent-based pigment ink.
- Various printing methods can be applied as a method for printing on the receiving substrate of the present invention using the pigment ink, but it is preferable to employ an inkjet printing method, a screen printing method, a letterpress reverse printing method, or a gravure offset printing method. .
- the receiving substrate of the present invention has excellent printability for conductive ink containing a conductive substance as the fluid, and is required when forming a conductive pattern such as an electronic circuit, for example. It is possible to print fine lines having a width of about 0.01 ⁇ m to 200 ⁇ m, preferably about 0.01 ⁇ m to 150 ⁇ m without causing bleeding (thin lineability). Therefore, the receiving substrate of the present invention is formed of electronic circuits using silver ink or the like, formation of organic solar cells or electronic book terminals, organic EL, organic transistors, flexible printed boards, RFID, etc. It can also be suitably used in the field of printed electronics such as wiring for electromagnetic shielding of plasma displays.
- the receiving substrate (conductive ink receiving substrate) of the present invention that can be used for forming the conductive pattern is similar to the above in that the receiving layer-forming composition is formed on part or all of the surface of various supports. It has a receiving layer formed using.
- the receptor layer may be laminated on a support, but a part of the receptor layer may be impregnated in the support.
- the said receiving layer may be provided in either the single side
- the composition for forming a receiving layer is applied to and impregnated part or all of one side or both sides of a support, and then contained in the composition for forming a conductive receiving layer. It can be manufactured by removing the medium (B).
- Examples of the support suitable for laminating the receptor layer in the production of the conductive pattern include polyimide resin, polyamideimide resin, polyamide resin, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, acrylonitrile-butadiene- Acrylic resins such as styrene (ABS) and poly (meth) methyl acrylate, polyvinylidene fluoride, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polycarbonate, polyethylene, polypropylene, polyurethane, cellulose nanofiber, silicon, ceramics, glass, etc. Supports made of these materials, porous supports made of these materials, supports made of metals such as steel plates and copper, and the like can be used.
- the support generally used as a support in forming a conductive pattern such as a circuit board, from polyimide resin, polyethylene terephthalate, polyethylene naphthalate, glass, cellulose nanofiber, etc. It is preferable to use a support.
- substrates made of polyimide resin, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, acrylonitrile-butadiene-styrene (ABS), acrylic resin, glass, etc. are generally difficult to adhere, so resins, etc. Is often difficult to adhere.
- the support when used for applications that require flexibility, it is possible to use a material that is relatively flexible and capable of being bent. It is preferable for obtaining a final product. Specifically, it is preferable to use a film or sheet-like support formed by uniaxial stretching or the like.
- the film or sheet-like support examples include a polyethylene terephthalate film, a polyimide film, and a polyethylene naphthalate film.
- a known and commonly used method can be used, for example, gravure method, coating method, screen method, roller method.
- a rotary method, a spray method, an ink jet method, or the like can be applied.
- the method for removing the aqueous medium (B) that can be contained in the composition after coating or impregnating the support layer-forming composition of the present invention on a part or all of the surface of the support is particularly limited.
- a method of drying using a dryer is common.
- the drying temperature may be set to a temperature that can volatilize the solvent and does not adversely affect the support.
- the amount of the composition for forming the receiving layer on the surface of the support is determined based on the area of the support in consideration of the amount of the solvent contained in the fluid such as conductive ink and the thickness of the conductive pattern.
- the resin solid content is preferably in the range of 0.01 g / m 2 to 20 g / m 2 , taking into account the absorbability of the solvent in the fluid and the production cost, 0.01 g / m 2 to 10 g / m. 2 is particularly preferred.
- the fine-line property of a receiving base material can be improved further by increasing the adhesion amount of the said composition for receiving layer formation to the support body surface.
- the texture of the receiving base material tends to be slightly hard.
- the texture is generally 0.02 g / m 2. It is preferable to make it relatively thin, about ⁇ 10 g / m 2 .
- it may be used in such a mode that it becomes a relatively thick film of about 10 g / m 2 to 100 g / m 2 . ⁇ The lower limit of film thickness has been changed.
- the receiving substrate of the present invention obtained by the above method can be suitably used even when a conductive ink is used as the fluid.
- a conductive ink for example, in the printed electronics field described above, it is suitable only for the formation of a conductive pattern or the like.
- the receiving substrate and the circuit forming substrate can be printed using conductive ink as the fluid. Specifically, printing is carried out using a conductive ink on the receiving layer constituting the receiving substrate, and then a baking step is performed, for example, in the conductive ink on the receiving substrate. A conductive pattern made of a conductive material made of a metal such as silver can be formed.
- the viscosity measured by a B-type viscometer at about 25 ° C. is about 0.1 mPa ⁇ s to 500,000 mPa ⁇ s, preferably about 0.
- the fluid is printed by an inkjet printing method, it is preferable to use a fluid having a viscosity range of 0.5 mPa ⁇ s to 10000 mPa ⁇ s.
- the conductive ink for example, an ink containing a conductive substance, a solvent, and, if necessary, an additive such as a dispersant can be used.
- a transition metal or a compound thereof can be used as the conductive substance.
- an ionic transition metal for example, it is preferable to use a transition metal such as copper, silver, gold, nickel, palladium, platinum, cobalt, and to use silver, gold, copper, or the like. It is more preferable because a conductive pattern having low electric resistance and strong against corrosion can be formed.
- the conductive material it is preferable to use a particulate material having an average particle diameter of about 1 nm to 50 nm.
- the said average particle diameter means a center particle diameter (D50), and shows the value at the time of measuring with a laser diffraction scattering type particle size distribution measuring apparatus.
- the conductive substance such as metal is preferably contained in the range of 10% by mass to 60% by mass with respect to the total amount of the conductive ink.
- the solvent used for the conductive ink various organic solvents and an aqueous medium such as water can be used.
- the receiving substrate of the present invention can be suitably used when a solvent-based conductive ink is used.
- a solvent-based conductive ink mainly containing an organic solvent as a solvent of the conductive ink, an aqueous conductive ink mainly containing water as the solvent, and a conductive containing both the organic solvent and water.
- a suitable ink can be selected and used.
- the conductive ink containing both the organic solvent and water as the solvent of the conductive ink, and the solvent of the conductive ink It is preferable to use a solvent-based conductive ink mainly containing an organic solvent, and it is more preferable to use a solvent-based conductive ink mainly containing an organic solvent as the solvent of the conductive ink.
- the receiving layer of the receiving substrate of the present invention is used only as the organic solvent in combination with a conductive ink containing a polar solvent. This is preferable because it is possible to achieve a level of fineness that can be used for realizing higher density of electronic circuits and the like.
- Examples of the solvent used in the solvent-based conductive ink include methanol, n-propanol, isopropyl alcohol, n-butanol, isobutyl alcohol, sec-butanol, tert-butanol, heptanol, hexanol, octanol, nonanol, decanol, and undecanol.
- polar solvents use of a solvent having a hydroxyl group prevents bleeding and fine lineability of a conductive pattern and the like, and lack of a conductive substance contained in the conductive ink from the surface of the receiving layer. It is preferable for preventing the above.
- the solvent-based conductive ink can be used in combination with a ketone-based solvent such as acetone, cyclohexanone, methyl ethyl ketone, etc. in order to adjust physical properties.
- ester solvents such as ethyl acetate, butyl acetate, 3-methoxybutyl acetate, 3-methoxy-3-methyl-butyl acetate, hydrocarbon solvents such as toluene, especially hydrocarbon solvents having 8 or more carbon atoms
- nonpolar solvents such as octane, nonane, decane, dodecane, tridecane, tetradecane, cyclooctane, xylene, mesitylene, ethylbenzene, dodecylbenzene, tetralin, and trimethylbenzenecyclohexane can be used in combination as necessary.
- solvents such as mineral spirits and solvent naphtha,
- the receiving layer formed using the composition for forming a receiving layer of the present invention is preferably used in combination with a conductive ink containing a polar solvent
- the nonpolar solvent is preferably contained in the conductive ink. More preferably, it is 0% by mass to 40% by mass with respect to the total amount of the solvent contained.
- the same medium as the aqueous medium (B) can be used.
- the same medium as the aqueous medium (B) can be used.
- water may be used, or water and water-soluble medium may be used.
- a mixed solution of an ionic solvent may be used.
- the water-soluble solvent include alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, ethyl carbitol, ethyl cellosolve, butyl cellosolve, and polar solvents such as N-methylpyrrolidone. It is preferable in terms of preventing the fine line property and the loss of the conductive substance contained in the conductive ink from the surface of the receiving layer.
- the solvent contained in the conductive ink is preferably contained in the range of 40% by mass to 90% by mass with respect to the total amount of the conductive ink.
- the polar solvent is preferably contained in an amount of 40% by mass to 100% by mass with respect to the total amount of the solvent.
- various additives can be used as necessary for the conductive ink.
- a dispersant can be used from the viewpoint of improving dispersibility of the metal in the solvent.
- the dispersant examples include amine-based polymer dispersants such as polyethyleneimine and polyvinylpyrrolidone, hydrocarbon-based polymer dispersants having a carboxylic acid group in the molecule such as polyacrylic acid and carboxymethylcellulose, and polyvinyl alcohol.
- a polymer dispersant having a polar group such as a styrene-maleic acid copolymer, an olefin-maleic acid copolymer, or a copolymer having a polyethyleneimine moiety and a polyethylene oxide moiety in one molecule.
- the polyvinyl alcohol may be used as a dispersant even when a solvent-based conductive ink is used.
- Examples of a method for printing on the receiving substrate using the conductive ink include, for example, an ink jet printing method, a screen printing method, a letterpress reverse printing method or a gravure offset printing method, an offset printing method, a spin coating method, and a spray coating method. , Bar coating method, die coating method, slit coating method, roll coating method, dip coating method and the like.
- an ink jet printer As the ink jet printing method, what is generally called an ink jet printer can be used. Specific examples include Konica Minolta EB100 and XY100 (manufactured by Konica Minolta IJ Co., Ltd.), Dimatics Material Printer DMP-3000, Dimatics Material Printer DMP-2831 (manufactured by Fuji Film Co., Ltd.), and the like. .
- the screen printing method is a method in which a conductive ink is applied to the surface of the receiving layer by using a mesh-shaped screen plate.
- a conductive pattern having a predetermined pattern shape can be formed by printing a conductive pattern in a predetermined pattern shape using a metal screen plate generally called a metal mesh.
- the letterpress reverse printing method is a method in which a conductive ink is applied on a blanket to form a conductive ink application surface and transferred to the receiving layer.
- conductive ink is applied on the blanket to form a layer made of conductive ink.
- the conductive ink contacting the relief plate is transferred from the blanket onto the relief plate surface by pressing a relief plate provided with a plate corresponding to a predetermined pattern shape as necessary to the layer made of the conductive ink. Is done.
- the conductive ink remaining on the blanket is transferred to the surface of the receiving layer by bringing the blanket into contact with the receiving layer.
- a conductive pattern having a predetermined pattern can be formed.
- the gravure offset printing method for example, after supplying conductive ink to a groove portion of an intaglio printing plate having a predetermined pattern shape, the conductive ink is applied onto the blanket by pressing the blanket on the surface thereof. And then transferring the conductive ink on the blanket to the receiving layer.
- the intaglio printing plate for example, a gravure plate, a glass intaglio plate formed by etching a glass plate, or the like can be used.
- a blanket having a multilayer structure including a silicone rubber layer, a polyethylene terephthalate layer, a sponge-like layer, etc. can be used and is usually wound around a rigid cylinder called a blanket cylinder. Is used.
- Conductivity can be imparted to the printed matter that has been printed on the receiving substrate by the above-described method by closely contacting and joining the conductive substances contained in the conductive ink.
- the firing is preferably performed in the range of approximately 80 ° C. to 300 ° C. for approximately 2 minutes to 200 minutes.
- the firing may be performed in the air, but from the viewpoint of preventing oxidation of the metal, part or all of the firing step may be performed in a reducing atmosphere.
- the baking step can be performed using, for example, an oven, a hot air drying furnace, an infrared drying furnace, laser irradiation, flash lamp irradiation, microwave, or the like.
- the firing temperature is preferably in the range of approximately 80 ° C. to 300 ° C., more preferably 100 ° C. to 300 ° C., and particularly preferably 120 ° C. to 300 ° C.
- the upper limit of the temperature is preferably 200 ° C. or lower, more preferably 150 ° C. or lower.
- the conductive pattern is formed by the metal contained in the conductive ink on the surface of the printed matter obtained through the baking step.
- a conductive pattern can be used for circuit boards, integrated circuit boards, and the like of various electric products.
- the conductive pattern was plated with a metal such as copper in order to form a highly reliable wiring pattern capable of maintaining good electrical conductivity without causing disconnection or the like over a long period of time. Things can be used.
- a part of or the entire surface of the support has a receptor layer formed by using the receptor layer forming composition, and one surface of the receptor layer is formed.
- the plating nucleus is supported on a part or all by applying a plating nucleating agent, and after passing through a firing step or the like, if necessary, electrolytic plating treatment, electroless plating treatment, or further electrolysis after the electroless plating treatment What has a plating film formed by performing a plating process is mentioned.
- plating nucleating agent one corresponding to the conductive ink exemplified as the fluid can be used.
- a plating nucleus specifically, a conductive material dispersed in a solvent is used. Can do.
- Examples of the conductive substance used for the plating nucleating agent include metal particles exemplified as the conductive substance usable for the conductive ink, oxides of the metal, and those whose surface is coated with an organic substance. One or more types can be used.
- the metal oxide is usually in an inactive (insulating) state, but it can be exposed to the metal and treated with a reducing agent such as dimethylaminoborane to impart activity (conductivity). It becomes.
- examples of the metal whose surface is coated with the organic substance include those in which a metal is contained in resin particles (organic substance) formed by an emulsion polymerization method or the like. These are usually in an inactive (insulating) state, but by removing the organic substance using, for example, a laser or the like, it becomes possible to expose the metal and impart activity (conductivity).
- the conductive substance contained in the plating nucleating agent preferably has an average particle diameter in the range of about 10 nm to 1000 nm.
- the same solvents as those exemplified as the solvent such as an aqueous medium or an organic solvent usable for the conductive ink can be used.
- the electroless plating treatment step for example, a metal such as copper contained in the electroless plating solution by bringing the electroless plating solution into contact with the surface of a receiving substrate on which a plating nucleus such as palladium or silver is supported.
- a metal such as copper contained in the electroless plating solution by bringing the electroless plating solution into contact with the surface of a receiving substrate on which a plating nucleus such as palladium or silver is supported.
- a plating nucleus such as palladium or silver
- a material containing a conductive material made of a metal such as copper, nickel, chromium, cobalt, tin, a reducing agent, and a solvent such as an aqueous medium or an organic solvent may be used. it can.
- reducing agent for example, dimethylaminoborane, hypophosphorous acid, sodium hypophosphite, dimethylamine borane, hydrazine, formaldehyde, sodium borohydride, phenols and the like can be used.
- monocarboxylic acids such as acetic acid and formic acid
- dicarboxylic acids such as malonic acid, succinic acid, adipic acid, maleic acid, fumaric acid
- malic acid lactic acid, glycolic acid Hydroxycarboxylic acids such as gluconic acid and citric acid
- amino acids such as glycine, alanine, iminodiacetic acid, arginine, aspartic acid and glutamic acid
- It may contain complexing agents such as organic acids such as carboxylic acids, soluble salts of these organic acids (sodium salts, potassium salts, ammonium salts, etc.), amines such as ethylenediamine, diethylenetriamine, and triethylenetetramine.
- the temperature of the electroless plating solution when the electroless plating solution is brought into contact with the surface of the receiving substrate on which the plating nucleus in the plating nucleating agent is supported is generally in the range of 20 ° C. to 98 ° C. preferable.
- the electrolytic plating treatment step may be performed by applying an electrolytic plating solution to the surface (x) of the receiving substrate on which the plating nucleus is supported or the surface (y) of the electroless plating film formed by the electroless treatment, for example.
- an electrolytic plating solution By energizing in the state of contact, a metal such as copper contained in the electrolytic plating solution can be used for the surface (x) of the receiving base placed on the negative electrode or the electroless plating film formed by the electroless treatment. It is a step of depositing on the surface (y) to form an electrolytic plating film (metal film).
- a solution containing a conductive substance made of a metal such as copper, nickel, chromium, cobalt, tin, sulfuric acid, and an aqueous medium can be used.
- the temperature of the electrolytic plating solution when the electrolytic plating solution is brought into contact with the surface of the receiving substrate on which the plating nucleus in the plating nucleating agent is supported is preferably in the range of about 20 ° C to 98 ° C.
- a strong acid or strong alkaline plating solution as described above is often used. It often causes peeling of the receiving layer from the support.
- the receptor layer is peeled off from the support in the plating treatment step for the cross-linked structure formed in the receiving layer. Will not cause.
- the support is made of a polyimide resin or the like, it does not cause peeling of the receiving layer, and therefore can be used very suitably for the production of the conductive pattern.
- the conductive pattern as described above is, for example, the formation of an electronic circuit using silver ink or the like, an organic solar cell or an electronic book terminal, an organic EL, an organic transistor, a flexible printed circuit board, an RFID, etc. It can be suitably used for forming and forming a conductive pattern, more specifically, a circuit board in manufacturing an electromagnetic wave shield wiring of a plasma display.
- the conductive pattern obtained by the above method after printing using a fluid such as conductive ink or plating nucleating agent, the conductive pattern obtained by forming a crosslinked structure in the receiving layer, Silver ink, etc., because it can provide excellent durability at a level that can maintain good electrical conductivity without causing peeling of the receptor layer from the support, etc., even after undergoing a plating process
- a copper-clad laminate is generally used.
- CCL Copper Clad Laminate
- FPC flexible printed circuit boards
- TAB automatic tape bonding
- COF chip-on-film
- PWB printed wiring boards
- Example 1 In a nitrogen-substituted reaction vessel equipped with a thermometer, a nitrogen gas inlet tube, and a stirrer, 6.3 parts by mass of 2,2-dimethylolpropionic acid and an isocyanurate of 4,4′-diphenylmethane diisocyanate 71. After preparing an isocyanate compound by reacting 1 part by mass with methyl ethyl ketone, 17.8 parts by mass of phenol as a blocking agent was supplied to the reaction vessel and reacted, thereby allowing the block polyisocyanate (A-1) to react. A solvent solution was prepared.
- Example 2 In a nitrogen-substituted reaction vessel equipped with a thermometer, a nitrogen gas inlet tube, and a stirrer, 6.1 parts by mass of 2,2-dimethylolpropionic acid, 2.8 parts by mass of ethylene glycol, and tolylene diisocyanate An isocyanate compound was prepared by reacting 70.8 parts by mass of an isocyanurate body in methyl ethyl ketone, and then 15.7 parts by mass of methyl ethyl ketone oxime as a blocking agent was supplied to the reaction vessel and reacted. A solvent solution of (A-2) was prepared.
- Example 3 In a nitrogen-substituted reaction vessel equipped with a thermometer, a nitrogen gas inlet tube, and a stirrer, 8.2 parts by mass of 2,2-dimethylolpropionic acid and 64.2 parts by mass of isocyanurate of tolylene diisocyanate Is reacted in methyl ethyl ketone to prepare an isocyanate compound, and then 21.4 parts by weight of methyl ethyl ketone oxime as a blocking agent is supplied to the reaction vessel and reacted to form a solvent solution of the blocked polyisocyanate (A-3). Prepared.
- Example 4 In a nitrogen-substituted reaction vessel equipped with a thermometer, a nitrogen gas inlet tube, and a stirrer, 5.6 parts by mass of 2,2-dimethylolpropionic acid, 3.7 parts by mass of 1,4-butanediol, An isocyanate compound is prepared by reacting 62.9 parts by mass of an isocyanurate of hexamethylene diisocyanate in methyl ethyl ketone, and then 23.5 parts by mass of ⁇ -caprolactam is supplied as a blocking agent to the reaction vessel and reacted. To prepare a solvent solution of the blocked polyisocyanate (A-4).
- Example 5 In a nitrogen-substituted reaction vessel equipped with a thermometer, a nitrogen gas inlet tube, and a stirrer, 41.8 parts by mass of polyethylene glycol having a number average molecular weight of 1000 and 42.2 parts by mass of isocyanurate of hexamethylene diisocyanate were obtained. After preparing an isocyanate compound by reacting in methyl ethyl ketone, 16.1 parts by mass of 3,5-dimethylpyrazole as a blocking agent was supplied to the reaction vessel and reacted, thereby allowing the block polyisocyanate (A-5) to react. A solvent solution was prepared.
- Example 6 In a nitrogen-substituted reaction vessel equipped with a thermometer, a nitrogen gas inlet tube, and a stirrer, 6.3 parts by mass of 2,2-dimethylolpropionic acid and an isocyanurate of 4,4′-diphenylmethane diisocyanate 71. After preparing an isocyanate compound by reacting 1 part by mass with methyl ethyl ketone, 17.8 parts by mass of phenol was supplied as a blocking agent to the reaction vessel and reacted, thereby allowing the block polyisocyanate (A-6) to react. A solvent solution was prepared. Thereafter, methyl ethyl ketone was supplied and the solid content thereof was adjusted to obtain a receiving layer forming composition (solid content of 20% by mass) containing block polyisocyanate (A-6) and methyl ethyl ketone.
- a bar coater was applied to the surface of the polyimide film (Kapton 200H, Toray DuPont Kapton 200H, thickness 50 ⁇ m) so that the dry film thickness was 0.1 ⁇ m.
- Each of the receiving base materials having a receiving layer formed on the surface of the polyimide film was prepared by applying the coating material and drying at 70 ° C. for 3 minutes using a hot air dryer.
- the product is then washed with 100 ml of 5% by weight aqueous hydrochloric acid, then with 100 ml of saturated aqueous sodium bicarbonate solution and then with 100 ml of saturated aqueous sodium chloride solution, dried over anhydrous magnesium sulfate, filtered, After concentration, washing with hexane several times, filtration and drying under reduced pressure at 80 ° C., methoxypolyethylene glycol having p-toluenesulfonyloxy group was obtained.
- a mixed solvent of 200 ml of isopropyl alcohol and 200 ml of hexane was added to the silver dispersion and stirred for 2 minutes, followed by centrifugal concentration at 3000 rpm for 5 minutes.
- a mixed solvent of 50 ml of isopropyl alcohol and 50 ml of hexane was added to the precipitate and stirred for 2 minutes, followed by centrifugal concentration at 3000 rpm for 5 minutes.
- 20 g of water was further added to the precipitate, followed by stirring for 2 minutes, and the organic solvent was removed under reduced pressure.
- a conductive ink 1 usable for a conductive ink for inkjet printing was prepared. (Silver content 20% by mass, polyethyleneimine 1% by mass, viscosity 10 mPa ⁇ s).
- the conductive ink 1 is coated on the surface of each receiving substrate using an ink jet printer (ink jet tester EB100 manufactured by Konica Minolta IJ Co., Ltd., evaluation printer head KM512L, discharge amount 42 pl) and a line width of 100 ⁇ m and a film thickness of 0
- a printed matter 1 was obtained by printing about 1 cm of a 5 ⁇ m straight line and then drying at 200 ° C. for 30 minutes.
- the conductive ink 1 is printed on the surface of each receiving substrate using a similar ink jet printer as described above, and a straight line having a line width of 1 mm and a thickness of 0.5 ⁇ m is printed by about 1 cm, and then at 200 ° C.
- the printed matter 2 was obtained by drying for 30 minutes.
- the boundary between the printed part and the non-printed part in that part Is partially unclear, but the entire line portion is smooth and usable level is “C”, the range of about 1/3 to 1/2 of the outer edge of the printed portion (line portion) In this part, the border between the printed part and the non-printed part is partially unclear, and the line part is flat at the outer edge part and the central part. "D” was not, and bleeding was confirmed in the range of about 1/2 or more of the outer edge of the printed part (line part), and the boundary between the printed part and the non-printed part was partially unclear at that part Thus, what was not smooth at the outer edge portion and the central portion of the line portion was evaluated as “E”.
- a cellophane adhesive tape (manufactured by Nichiban Co., Ltd., CT405AP-24, 24 mm) is pressure-bonded onto the pattern (printing portion) formed on the surface of the printed matter 2 with a finger, and the cellophane adhesive tape is then attached It peeled in the direction 90 degree
- A indicates that the silver contained in the conductive ink and the receiving layer were not attached to the adhesive surface of the peeled cellophane adhesive tape, and silver in a range of less than about 5% with respect to the adhesive tape application area.
- the receiving layer peeled from the support, and “B” was attached to the adhesive tape, and the silver and the receiving layer in the range of about 5% or more and less than 50% with respect to the sticking area of the adhesive tape were peeled from the support,
- the adhesive attached to the adhesive tape was evaluated as “C”, and the silver and the receiving layer in the range of about 50% or more of the adhesive tape applied area were peeled off from the support, and the adhesive attached to the adhesive tape was evaluated as “D”. .
- An activator (A screen A220 manufactured by Okuno Pharmaceutical Co., Ltd.) is applied to the pattern (printing part) formed on the surface of the printed matter 2 obtained above, and the activity of the plating nucleus under conditions of 55 ° C. ⁇ 5 minutes. The treatment was performed.
- an electroless copper plating agent (OPC-750 manufactured by Okuno Pharmaceutical Co., Ltd.) was applied to the surface subjected to the activation treatment, and an electroless copper plating treatment was performed at 20 ° C. for 20 minutes.
- a conductive pattern in which a plating film made of copper was formed on the surface on which the plating nucleus was carried was obtained.
- a copper having a thickness of 8 ⁇ m was used.
- the pattern (printing part) formed on the surface of the printed matter 2 obtained above is set as a cathode, phosphorous copper is set as an anode, and an electroplating solution containing copper sulfate is used for 15 minutes at a current density of 2 A / dm2.
- an electroplating solution containing copper sulfate is used for 15 minutes at a current density of 2 A / dm2.
- the electroplating solution 70 g / liter of copper sulfate, 200 g / liter of sulfuric acid, 50 mg / liter of chloride ion, and 5 g / liter of Top Lucina SF (brightener manufactured by Okuno Pharmaceutical Co., Ltd.) were used.
- the peel strength of the conductive pattern provided with the plating layer was measured by a method based on IPC-TM-650 and NUMBER 2.4.9.
- the lead width used for the measurement was 1 mm, and the peel angle was 90 °.
- the peel strength tends to show a higher value as the thickness of the plating layer increases, but the peel strength measurement in the present invention is based on the measurement value at a thickness of 8 ⁇ m of the plating layer that is currently widely used. Carried out.
- MDI nurate represents an isocyanurate of 4,4'-diphenylmethane diisocyanate
- TDI nurate represents an isocyanurate of tolylene diisocyanate
- HDI nurate represents an isocyanurate of hexamethylene diisocyanate.
- Superflex 150 Latex manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
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- Chemical Kinetics & Catalysis (AREA)
- Wood Science & Technology (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Dispersion Chemistry (AREA)
- Manufacturing Of Printed Wiring (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Ink Jet Recording Methods And Recording Media Thereof (AREA)
- Laminated Bodies (AREA)
Abstract
Description
本発明の受容層形成用組成物は、前記ブロックイソシアネート(A)等の固形分を溶解または分散しうる溶媒を含有するものであってもよい。
前記3級アミノ基の一部または全てを中和する際に使用することができる酸としては、例えば、酢酸、プロピオン酸、乳酸、マレイン酸などの有機酸、スルホン酸、メタンスルホン酸等の有機スルホン酸、及び、塩酸、硫酸、オルトリン酸、オルト亜リン酸等の無機酸を単独または2種以上を組み合わせて使用してもよい。導電性パターン等を形成する場合には、塩素や硫黄が通電性等を阻害しうる場合があるため、酢酸、プロピオン酸、乳酸、マレイン酸等を使用することが好ましい。
→膜厚の下限を変更しました。
温度計、窒素ガス導入管、攪拌器を備えた窒素置換された反応容器中で、2,2-ジメチロールプロピオン酸6.3質量部と、4,4’-ジフェニルメタンジイソシアネートのイソシアヌレート体71.1質量部とを、メチルエチルケトン中で反応させることによってイソシアネート化合物を調製した後、前記反応容器にブロック剤としてフェノール17.8質量部を供給し反応させることによって、ブロックポリイソシアネート(A-1)の溶剤溶液を調製した。
温度計、窒素ガス導入管、攪拌器を備えた窒素置換された反応容器中で、2,2-ジメチロールプロピオン酸6.1質量部と、エチレングリコール2.8質量部と、トリレンジイソシアネートのイソシアヌレート体70.8質量部とを、メチルエチルケトン中で反応させることによってイソシアネート化合物を調製した後、前記反応容器にブロック剤としてメチルエチルケトンオキシム15.7質量部を供給し反応させることによって、ブロックポリイソシアネート(A-2)の溶剤溶液を調製した。
温度計、窒素ガス導入管、攪拌器を備えた窒素置換された反応容器中で、2,2-ジメチロールプロピオン酸8.2質量部と、トリレンジイソシアネートのイソシアヌレート体64.2質量部とを、メチルエチルケトン中で反応させることによってイソシアネート化合物を調製した後、前記反応容器にブロック剤としてメチルエチルケトンオキシム21.4質量部を供給し反応させることによって、ブロックポリイソシアネート(A-3)の溶剤溶液を調製した。
温度計、窒素ガス導入管、攪拌器を備えた窒素置換された反応容器中で、2,2-ジメチロールプロピオン酸5.6質量部と、1,4-ブタンジオール3.7質量部と、ヘキサメチレンジイソシアネートのイソシアヌレート体62.9質量部とを、メチルエチルケトン中で反応させることによってイソシアネート化合物を調製した後、前記反応容器にブロック剤としてε-カプロラクタム23.5質量部を供給し反応させることによって、ブロックポリイソシアネート(A-4)の溶剤溶液を調製した。
温度計、窒素ガス導入管、攪拌器を備えた窒素置換された反応容器中で、数平均分子量1000のポリエチレングリコール41.8質量部と、ヘキサメチレンジイソシアネートのイソシアヌレート体42.2質量部とを、メチルエチルケトン中で反応させることによってイソシアネート化合物を調製した後、前記反応容器にブロック剤として3,5-ジメチルピラゾール16.1質量部を供給し反応させることによって、ブロックポリイソシアネート(A-5)の溶剤溶液を調製した。
温度計、窒素ガス導入管、攪拌器を備えた窒素置換された反応容器中で、2,2-ジメチロールプロピオン酸6.3質量部と、4,4’-ジフェニルメタンジイソシアネートのイソシアヌレート体71.1質量部とを、メチルエチルケトン中で反応させることによってイソシアネート化合物を調製した後、前記反応容器にブロック剤としてフェノール17.8質量部を供給し反応させることによって、ブロックポリイソシアネート(A-6)の溶剤溶液を調製した。その後、メチルエチルケトンを供給しその固形分を調整することによって、ブロックポリイソシアネート(A-6)とメチルエチルケトンとを含有する受容層形成組成物(固形分20質量%)を得た。
受容層形成用組成物として、スーパーフレックス150(第一工業製薬株式会社製、ラテックス)を使用した。
実施例及び比較例に記載の受容層形成用組成物を、乾燥膜厚が0.1μmになるように、ポリイミドフィルム(東レ・デュポン株式会社製Kapton200H,厚さ50μm)の表面に、バーコーターを用いて塗布し、熱風乾燥機を用いて70℃で3分間乾燥することによって、ポリイミドフィルムの表面に受容層の形成された受容基材をそれぞれ作製した。
窒素雰囲気下、メトキシポリエチレングリコール(数平均分子量2,000)20g、ピリジン8.0g及びクロロホルム20mlを含む混合物に、p-トルエンスルホン酸クロライド9.6gを含むクロロホルム(30ml)溶液を、氷冷撹拌しながら30分間滴下した後、浴槽温度40℃で4時間攪拌し、クロロホルム50mlを混合した。
前記導電性インク1を、それぞれの受容基材の表面に、インクジェットプリンター(コニカミノルタIJ株式会社製インクジェット試験機EB100、評価用プリンタヘッドKM512L、吐出量42pl)を用い、線幅100μmで膜厚0.5μmの直線を約1cm印刷し、次いで200℃の条件下で30分間乾燥することによって、印刷物1を得た。
前記方法で得た印刷物1の表面に形成された線幅100μmのパターン(印刷部)を、光学顕微鏡((株)キーエンス製デジタルマイクロスコープVHX-100)を用いて観察し、その印刷部のにじみの有無を確認した。
前記印刷物2の表面に形成されたパターン(印刷部)上にセロハン粘着テープ(ニチバン株式会社製,CT405AP-24,24mm)を指で圧着し貼付した後、前記セロハン粘着テープを、印刷物2の表面に対して90度方向に剥離した。剥離したセロハン粘着テープの粘着面を目視で観察し、その付着物の有無に基づいて前記密着性を評価した。
前記で得た印刷物2の表面に形成されたパターン(印刷部)に、活性化剤(奥野製薬工業株式会社製エースクリーンA220)を塗布し、55℃×5分間の条件下でめっき核の活性化処理を行った。
前記で得た印刷物2の表面に形成されたパターン(印刷部)を陰極に設定し、含リン銅を陽極に設定し、硫酸銅を含む電気めっき液を用いて電流密度2A/dm2で15分間電気めっきを行うことによって、印刷物2の表面に、厚み8μmの銅めっき層が積層された導電性パターンを得た。前記電気めっき液としては、硫酸銅70g/リットル、硫酸200g/リットル、塩素イオン50mg/リットル、トップルチナSF(奥野製薬工業株式会社製の光沢剤)5g/リットルを使用した。
前記めっき層が設けられた導電性パターンのピール強度測定は、IPC-TM-650、NUMBER2.4.9に準拠した方法により行った。測定に用いたリード幅は1mm、そのピールの角度は90°とした。なお、ピール強度は、前記めっき層の厚みが厚くなるほど高い値を示す傾向にあるが、本発明でのピール強度の測定は、現在汎用されているめっき層の厚さ8μmにおける測定値を基準として実施した。
Claims (15)
- ブロックイソシアネート(A)を、受容層形成用組成物の固形分に対して50質量%~100質量%含有することを特徴とする受容層形成用組成物。
- 前記ブロックイソシアネート(A)が、1,000~5,000の範囲の数平均分子量を有するものである請求項1に記載の受容層形成用組成物。
- 前記ブロックイソシアネート(A)が、芳香族構造を有するものである請求項1に記載の受容層形成用組成物。
- 前記ブロックイソシアネート(A)は、イソシアネート基がブロック剤によって封鎖された官能基[a]を有するものであって、前記官能基[a]は70℃~200℃の範囲で加熱されることによって前記ブロック剤が解離し、イソシアネート基を生成するものである請求項1に記載の受容層形成用組成物。
- 前記ブロックイソシアネート(A)が、前記官能基[a]を350g/mol~600g/molの範囲で有するものである請求項4に記載の受容層形成用組成物。
- さらに水性媒体(B)を含有する請求項1に記載の受容層形成用組成物。
- 前記ブロックイソシアネート(A)が親水性基を有するブロックイソシアネートである請求項1または6に記載の受容層形成用組成物。
- 前記受容層形成用組成物が、導電性物質または顔料を含有する流動体を受容する層を形成するものである請求項1に記載の受容層形成用組成物。
- 支持体表面の一部または全部に、ブロックイソシアネート(A)を含有する受容層形成用組成物を用いて形成された受容層を有することを特徴とする受容基材。
- 請求項9に記載の受容基材を構成する受容層上に、導電性物質または顔料を含有する流動体によって印刷の施された印刷物。
- 請求項9に記載の受容基材を構成する受容層上に、導電性物質を含有する導電性インク、または、導電性物質を含有するめっき核剤からなる流動体を用いて印刷の施された導電性パターン。
- 前記流動体を印刷することによって形成された印刷部の表面に、電解めっきまたは無電解めっき処理を施すことによって得られるものである請求項11に記載の導電性パターン。
- 請求項11または12に記載の導電性パターンを有する電気回路。
- 支持体の表面の一部または全部に、ブロックイソシアネート(A)を含有する受容層形成用組成物を塗布し、前記ブロックイソシアネート(A)を構成するブロック剤が解離しない条件で乾燥することによって、導電性物質または顔料を含有する流動体を受容するための受容層を形成し、次いで、前記受容層の表面に、前記流動体を印刷し、次いで前記加熱することによって、前記ブロック剤が解離し生成したイソシアネート基を自己架橋反応させることを特徴とする印刷物の製造方法。
- 支持体の表面の一部または全部に、ブロックイソシアネート(A)を含有する受容層形成用組成物を塗布し、前記ブロックイソシアネート(A)を構成するブロック剤が解離しない条件で乾燥することによって、導電性物質を含有する流動体を受容するための受容層を形成し、前記受容層の表面に、前記流動体を印刷し、次いで前記加熱することによって、前記ブロック剤が解離し生成したイソシアネート基を自己架橋反応させ、次いで前記受容層表面に形成された前記印刷部をめっき処理することを特徴とする導電性パターンの製造方法。
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DE112014000533.9T DE112014000533T5 (de) | 2013-01-23 | 2014-01-16 | Absorbierende Schicht-bildende Zusammensetzung und absorbierendes Substrat, Druckerzeugnis, Leiterbild und elektrischer Stromkreis, hergestellt unter Verwendung derselben |
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KR1020157009556A KR101594565B1 (ko) | 2013-01-23 | 2014-01-16 | 수용층 형성용 조성물, 그것을 사용해서 얻어지는 수용 기재, 인쇄물, 도전성 패턴 및 전기 회로 |
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