WO2013035582A1 - 受容層形成用樹脂組成物ならびに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
受容層形成用樹脂組成物ならびに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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- WO2013035582A1 WO2013035582A1 PCT/JP2012/071683 JP2012071683W WO2013035582A1 WO 2013035582 A1 WO2013035582 A1 WO 2013035582A1 JP 2012071683 W JP2012071683 W JP 2012071683W WO 2013035582 A1 WO2013035582 A1 WO 2013035582A1
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- receiving layer
- forming
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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
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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
- B41M5/5218—Macromolecular coatings characterised by inorganic additives, e.g. pigments, clays
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- 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
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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
-
- 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
- B41M5/5254—Macromolecular coatings characterised by the use of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
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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
- B41M5/5281—Polyurethanes or polyureas
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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
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
- C08L33/12—Homopolymers or copolymers of methyl methacrylate
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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
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/24—Homopolymers or copolymers of amides or imides
- C08L33/26—Homopolymers or copolymers of acrylamide or methacrylamide
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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
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
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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
-
- 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
- H05K1/036—Multilayers with layers of different types
-
- 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
- H05K1/097—Inks comprising nanoparticles and specially adapted for being sintered at low temperature
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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
- H05K3/10—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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
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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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
- Y10T428/24893—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] including particulate material
- Y10T428/24901—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] including particulate material including coloring matter
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
Definitions
- the present invention relates to a receiving layer forming resin composition capable of receiving a fluid such as ink ejected by various printing methods including an ink jet printing method, a receiving substrate, and a printed matter such as a conductive pattern.
- ink-jet printer-related industries where growth has been remarkable, have dramatically improved the performance of ink-jet printers and improved ink, making it easy to produce high-definition and clear printability images similar to silver halide photographs. It is becoming possible to obtain. For this reason, ink jet printers are starting to be used not only in homes but also in various fields including the production of large advertising signs.
- the pigment ink having the high color developability is used, depending on the composition of the ink receiving layer, a print image having high color density and excellent printability can be formed, such as causing ink bleeding. There were cases where it was difficult.
- 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 or a screen printing method, 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 an acrylic resin can be used as the latex layer (see Patent Document 1).
- the ink receiving layer made of the latex layer constituting the conductive pattern may cause bleeding of the conductive ink, unevenness of the printing thickness, etc.
- 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. Further, when the baking process is performed, excessive swelling and deformation of the latex layer, which is an ink-receiving layer, are likely to be caused. In addition, since 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 that, among the receiving layers capable of carrying a fluid such as ink, a receiving layer having excellent adhesion to various supports can be formed, causing bleeding of the fluid such as ink. It is an object of the present invention to provide a resin composition for forming a receiving layer capable of forming a receiving layer having excellent printability without any problems.
- the second problem to be solved by the present invention is that, among the receiving layers capable of supporting a fluid such as conductive ink, a receiving layer having excellent adhesion to the support can be formed. Even if it is possible to draw fine lines at a level that can be used to achieve higher density of electronic circuits etc. without causing blurring or repellency, and even if chemicals such as plating chemicals or various organic solvents adhere
- a resin composition for forming a receiving layer capable of forming a printed matter such as a conductive pattern having a level of durability capable of maintaining good electrical conductivity without causing peeling of the receiving layer from the support That is.
- the present invention is a resin composition for forming a receiving layer containing a urethane resin (A), a vinyl polymer (B), and an aqueous medium (C), wherein the urethane resin (A) is the urethane resin.
- the present invention relates to a resin composition for forming a receiving layer characterized by having an aliphatic cyclic structure of 2,000 mmol / kg to 5,500 mmol / kg and a hydrophilic group with respect to the total amount of the resin (A). Is.
- the resin composition for forming a receiving layer of the present invention has excellent adhesion to various supports, and is excellent in high color printability without causing bleeding of a fluid such as pigment ink. Since it can form a printed image, it can be used, for example, in a recording medium used for manufacturing advertisements, signs, signs, etc. that can be installed indoors and outdoors.
- a receiving layer having excellent adhesion between the receiving layer and the support can be formed, and high density such as an electronic circuit can be formed without causing bleeding of the conductive ink.
- a conductive ink containing a conductive substance such as silver can be used because it can provide a thin line with a level capable of drawing a thin line at a level that can be used for the realization of, for example, and can form a receiving layer with excellent durability.
- the receptor layer formed using the resin composition for forming a receptor layer of the present invention is printed on the receptor substrate of the present invention using a fluid such as conductive ink or plating nucleating agent, and then heated.
- a fluid such as conductive ink or plating nucleating agent
- the resin composition for forming a receiving layer of the present invention comprises a urethane resin having an aliphatic cyclic structure of 2,000 mmol / kg to 5,500 mmol / kg and a hydrophilic group based on the total amount of the urethane resin (A) ( A), a vinyl polymer (B), an aqueous medium (C), and optionally containing other additives.
- the resin composition for forming the receiving layer exclusively absorbs the solvent in the fluid when the fluid containing the conductive material or the pigment comes into contact with the receiving layer that carries the conductive material or the pigment. It can be used for forming.
- the urethane resin (A) and the vinyl polymer (B) contained in the resin composition for forming a receiving layer may be present independently in the aqueous medium (C), and they are composite resin particles. It may exist in a state where (D) is formed.
- the composite resin particle (D) specifically refers to a resin particle formed by the urethane resin (A) in which a part or all of the vinyl polymer (B) is present.
- the vinyl polymer (B) may be dispersed in a plurality of particles in the urethane resin (A) particles, and the vinyl polymer (B) as a core layer and a shell layer
- core-shell type composite resin particles composed of the urethane resin (A) having a hydrophilic group as
- said composite resin particle (D) it is preferable that the said vinyl polymer (B) is substantially completely covered with the said urethane resin (A), but it is not essential and does not impair the effect of this invention. In a range, a part of the vinyl polymer (B) may be present on the outermost part of the composite resin particle (D).
- the vinyl polymer (B) when the vinyl polymer (B) is more hydrophilic than the urethane resin (A), the vinyl polymer (B) is In the formed resin particles, a part or all of the urethane resin (A) may be present to form composite resin particles.
- the urethane resin (A) and the vinyl polymer (B) may form a covalent bond, but preferably do not form a bond.
- the composite resin particles (D) preferably have an average particle diameter in the range of 5 nm to 100 nm from the viewpoint of maintaining good water dispersion stability.
- the average particle diameter here refers to an average particle diameter on a volume basis measured by a dynamic light scattering method, as will be described later in Examples.
- the resin composition for forming a receiving layer of the present invention does not simply contain the urethane resin (A) and the vinyl monomer (B), and 2,000 mmol as the urethane resin (A). It is important to use a urethane resin having an aliphatic cyclic structure of / kg to 5,500 mmol / kg and a hydrophilic group.
- the resin composition for use may not be able to form a receiving layer excellent in adhesion to various supports.
- a strong alkali or strongly acidic substance is used in the plating process described later. Due to the influence of the plating agent comprising, there may be a case where the durability is remarkably lowered, for example, the receiving layer is peeled off from the support.
- a resin composition for forming a receiving layer obtained by using a urethane resin having an aliphatic cyclic structure content of 6,000 mmol / kg instead of the urethane resin (A), In some cases, it is not possible to form a receiving layer excellent in adhesion of the receiving layer to the support and durability in the plating process.
- the urethane resin (A) it is possible to use a resin having an aliphatic cyclic structure of 3,000 mmol / kg to 5,000 mmol / kg based on the total amount of the urethane resin (A). In particular, it is more preferable for preventing peeling of the receptor layer from the support in the plating process and improving durability.
- Examples of the aliphatic cyclic structure include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a propylcyclohexyl group, a tricyclo [5,2,1,0,2,6] decyl group, and a bicyclo [4].
- a cyclohexyl group, a norbornene group, an isobornyl group, and an adamantyl group are preferable for obtaining a printed matter such as a conductive pattern having excellent durability.
- the aliphatic cyclic structure as described above has a polyisocyanate having an aliphatic cyclic structure or an aliphatic cyclic structure as the polyisocyanate (a1) or polyol (a2) used in the production of the urethane resin (A).
- the polyol (a2-2) it can be introduced into the urethane resin (A).
- the polyisocyanate having an aliphatic cyclic structure and the aliphatic cyclic structure are preferably used.
- a urethane resin having an aliphatic cyclic structure derived from the polyol (a2-2) having a large improvement in the adhesion of the receptor layer to various supports it is particularly preferable to use a urethane resin having an aliphatic cyclic structure derived from the polyol (a2-2) having a large improvement in the adhesion of the receptor layer to various supports.
- the receptor layer from the support can be used even if it is immersed in a plating agent or the like made of a strong alkali or strong acid substance in the plating process described below. Since durability can be improved to the level which does not cause peeling, it is preferable.
- urethane resin (A) it is necessary to use a resin having a hydrophilic group from the viewpoint of imparting good water dispersion stability in the aqueous medium (C).
- 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.
- a carboxylate group partially or wholly neutralized with a basic compound or the like It is preferable to use a sulfonate group in order to impart good water dispersibility.
- Examples of basic compounds that can be used for neutralizing the anionic group include organic amines such as ammonia, triethylamine, pyridine, morpholine, alkanolamines such as monoethanolamine, sodium, potassium, lithium, and calcium.
- organic amines such as ammonia, triethylamine, pyridine, morpholine
- alkanolamines such as monoethanolamine, sodium, potassium, lithium, and calcium.
- a metal base compound is mentioned.
- 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 entire urethane resin (A), and 50 mmol / kg.
- the presence of 2,000 mmol / kg is more preferable in maintaining good water dispersion stability of the urethane resin (A) particles.
- a tertiary amino group etc. can be used, for example.
- the acid that can be used for neutralizing a part or all of the tertiary amino group include organic acids such as acetic acid, propionic acid, lactic acid, and maleic acid, sulfonic acid, methanesulfonic acid, and the like.
- Organic sulfonic acids and inorganic acids such as hydrochloric acid, sulfuric acid, orthophosphoric acid and orthophosphorous acid may be used alone or in combination of two or more.
- 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 urethane resin (A) can be produced by reacting a polyisocyanate (a1) and a polyol (a2) with a chain extender as necessary.
- polyisocyanate (a1) examples include aromatic structures such as 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate, crude diphenylmethane diisocyanate, phenylene diisocyanate, tolylene diisocyanate, and naphthalene diisocyanate.
- polyisocyanates such as hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, and other polyisocyanates having an aliphatic cyclic structure
- polyisocyanates such as hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, and other polyisocyanates having an aliphatic cyclic structure
- polystyrene resin As the polyol (a2) capable of reacting with the polyisocyanate (a1), a polyol (a2-1) having a hydrophilic group is essential, and if necessary, a polyol (a2-2) having an aliphatic cyclic structure, Other polyols (a2-3) can be used in combination.
- Examples of the polyol (a2-1) having a hydrophilic group include 2,2′-dimethylolpropionic acid, 2,2′-dimethylolbutanoic acid, 2,2′-dimethylolbutyric acid, and 2,2′-dimethylol.
- Carboxyl group-containing polyols such as valeric acid and polyols having sulfonic acid groups such as 5-sulfoisophthalic acid, sulfoterephthalic acid, 4-sulfophthalic acid, and 5 [4-sulfophenoxy] isophthalic acid can be used.
- polyol having a hydrophilic group examples include a polyester polyol having a hydrophilic group obtained by reacting the above-described polyol having a low molecular weight hydrophilic group with various polycarboxylic acids such as adipic acid. It can also be used.
- the hydrophilic group is preferably present in the range of 5 mmol / kg to 4,000 mmol / kg with respect to the total amount of the polyol (a2) used in the production of the urethane resin (A). More preferably, it is used in the range of 000 mmol / kg.
- a polyol (a2-2) having an aliphatic cyclic structure is preferable to use as the polyol (a2).
- Examples of the polyol (a2-2) having an aliphatic cyclic structure include 1,4-cyclohexanedimethanol, cyclobutanediol, cyclopentanediol, 1,4-cyclohexanediol, cycloheptanediol, cyclooctanediol, cyclohexanedi Methanol, tricyclo [5,2,1,0,2,6] decanedimethanol, bicyclo [4,3,0] -nonanediol, dicyclohexanediol, tricyclo [5,3,1,1] dodecanediol, bicyclo [4,3,0] nonanedimethanol, tricyclo [5,3,1,1] dodecanediethanol, spiro [3,4] octanediol, butylcyclohexanediol, 1,1'-bicyclohexylidenedio
- polyol (a2-2) having an aliphatic cyclic structure in addition to those described above, those obtained by reacting a polycarboxylic acid having an aliphatic cyclic structure with an aliphatic polyol may be used. it can.
- polycarboxylic acid having an aliphatic cyclic structure examples include 1,3-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and these Anhydrides or ester-forming derivatives thereof, among which polycarboxylic acids having an aliphatic cyclic structure such as 1,2-cyclohexanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid can be used.
- polycarboxylic acids having an aliphatic cyclic structure such as 1,2-cyclohexanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid can be used.
- 1,3-cyclopentanedicarboxylic acid 1,2-cyclohexanedicarboxylic acid
- 1,3-cyclohexanedicarboxylic acid 1,4-cyclo
- 1,3-propylene glycol dipropylene glycol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,5 -Hexanediol, 2,5-hexanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2-methyl-1,3
- aliphatic polyols such as propanediol.
- the aliphatic polyol may be used in combination with the polyol (a2-2) having the aliphatic cyclic structure and the polycarboxylic acid in an esterification reaction.
- polystyrene resin for example, a polycarbonate polyol having an aliphatic cyclic structure can be used.
- a polycarbonate polyol having an aliphatic cyclic structure for example, a polyol obtained by reacting the polyol (a1-1) having a low molecular weight aliphatic cyclic structure with dimethyl carbonate, phosgene or the like is used. be able to.
- polycarbonate polyol having an aliphatic cyclic structure a polycarbonate polyol having an aliphatic cyclic structure having a number average molecular weight of 800 to 3,000 is preferably used, and a number average molecular weight of 800 to 2,000 is preferably used. It is more preferable to use what has.
- polystyrene resin for example, a polyether polyol having an aliphatic cyclic structure can be used.
- the polyether polyol having an aliphatic cyclic structure for example, the above-described polyol (a1-1) having a low molecular weight aliphatic cyclic structure is used as an initiator, and an alkylene oxide such as ethylene oxide or propylene oxide is added.
- a polymerized product can be used.
- polyol (a2) other polyols (a2-3) can be used as necessary in addition to the above-described polyols.
- examples of the other polyol (a2-3) include polyester polyols, polyether polyols, and polycarbonate polyols other than those described above.
- polyester polyol examples include ring-opening polymerization of aliphatic polyester polyol and aromatic polyester polyol obtained by esterification reaction of low molecular weight polyol and polycarboxylic acid, and cyclic ester compounds such as ⁇ -caprolactone and ⁇ -butyrolactone. Polyester obtained by reaction, copolymerized polyester thereof, or the like can be used.
- Examples of the low molecular weight polyol that can be used in the production of the polyester polyol include ethylene glycol, 1,2-propanediol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, 3- Methyl-1,5-pentanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, glycerin, trimethylolpropane and the like can be used alone or in combination of two or more thereof.
- Ethylene glycol 1,2-propanediol
- 1,3-butanediol or 1,4-butanediol in combination with 3-methyl-1,5-pentanediol, neopentyl glycol, or the like.
- polycarboxylic acid examples include succinic acid, adipic acid, sebacic acid, dodecanedicarboxylic acid, azelaic acid, terephthalic acid, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, and anhydrides or ester-forming derivatives thereof. It is preferable to use an aliphatic polycarboxylic acid such as adipic acid.
- an aromatic polycarboxylic acid such as terephthalic acid, isophthalic acid, phthalic acid, or naphthalenedicarboxylic acid can be used as the polycarboxylic acid. .
- polyether polyol that can be used for the other polyol (a2-3)
- an alkylene oxide is addition-polymerized using one or more compounds having two or more active hydrogen atoms as an initiator. Things can be used.
- the initiator examples include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, trimethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, glycerin, Trimethylolethane, trimethylolpropane and the like can be used.
- alkylene oxide for example, ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, tetrahydrofuran, or the like can be used.
- Examples of the polycarbonate polyol that can be used for the other polyol (a2-3) include those obtained by reacting a carbonate with a polyol, and those obtained by reacting phosgene with bisphenol A or the like. Can do.
- carbonate ester methyl carbonate, dimethyl carbonate, ethyl carbonate, diethyl carbonate, cyclocarbonate, diphenyl carbonate, or the like can be used.
- polyol that can react with the carbonate ester examples include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol, 1,4-butanediol, 1,3-Butanediol, 1,2-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,5-hexanediol, 2,5-hexanediol, 1,6-hexanediol, 1,7-heptane Diol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 3-methyl-1,5-pentanediol, 2- Ethyl-1,3-hexanediol, 2-methyl-1,3-
- polyester polyol polyether polyol and polycarbonate polyol, those having a number average molecular weight of 500 to 4,000 are preferably used from the viewpoint of ease of mixing with the matrix resin, etc. More preferably, 500 is used.
- Examples of the other polyol (a2-3) include, in addition to the polyester polyol, polyether polyol and polycarbonate polyol, for example, ethylene glycol, 1,2-propanediol, 1,3-butanediol, , 4-butanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, neopentyl glycol, diethylene glycol, dipropylene glycol, glycerin, trimethylolpropane, Hydrophilic group-containing polyols such as methylolpropionic acid, acrylic polyols in which hydroxyl groups are introduced into acrylic copolymers, polybutadiene polyols that are butadiene copolymers containing hydroxyl groups in the molecules, hydrogenated polybutadiene polyols Le, ethylene - can be appropriately used partially saponified products of vinyl acetate copo
- chain extender that can be used when the urethane resin (A) is produced
- polyamine other active hydrogen atom-containing compounds, and the like can be used.
- polyamine examples include ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine, 2,5-dimethylpiperazine, isophoronediamine, 4,4'-dicyclohexylmethanediamine, 3,3'- Diamines such as dimethyl-4,4′-dicyclohexylmethanediamine, 1,4-cyclohexanediamine; N-hydroxymethylaminoethylamine, N-hydroxyethylaminoethylamine, N-hydroxypropylaminopropylamine, N-ethylaminoethylamine, N-methylaminopropylamine; diethylenetriamine, dipropylenetriamine, triethylenetetramine; hydrazine, N, N′-dimethylhydrazine, 1,6-hexamethylenebishydrazine; disuccinate Dorazide, adipic acid dihydrazide, glutaric acid dihydrazide, sebacic acid
- Examples of the other active hydrogen-containing compounds include ethylene glycol, diethylene recall, triethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, hexamethylene glycol, and saccharose.
- Glycols such as methylene glycol, glycerin and sorbitol; phenols such as bisphenol A, 4,4′-dihydroxydiphenyl, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxydiphenylsulfone, hydrogenated bisphenol A, hydroquinone , And water can be used.
- the chain extender is preferably used, for example, in a range where the equivalent ratio of the amino group and excess isocyanate group of the polyamine is 1.9 or less (equivalent ratio), 0.3 to 1.0 (equivalent It is more preferable to use it in the range of the ratio.
- the urethane resin (A) is a conventionally known method, for example, in the absence of a solvent or in the presence of an organic solvent, the polyisocyanate (a1), the polyol (a2), and, if necessary, the chain extender. It can manufacture by making it react.
- the reaction between the polyisocyanate (a1) and the polyol (a2) is preferably from 50 ° C. to 120 ° C., more preferably from 80 ° C. to 100 ° C.
- the polyisocyanate (a1) and the polyol (a2) are mixed at once or sequentially supplied by a method such as dropping one of them to the other and reacting for approximately 1 to 15 hours. It can be carried out.
- the aqueous dispersion of the urethane resin (A) is prepared by reacting the polyisocyanate (a1), the polyol (a2) and, if necessary, a chain extender by the method described above. If necessary, after neutralizing a part or all of the hydrophilic groups such as anionic groups of the urethane resin (A), the urethane resin is mixed with the aqueous medium (C). A urethane resin (A) aqueous dispersion in which (A) is dispersed or partially dissolved in the aqueous medium (C) can be obtained.
- a urethane prepolymer (A ′) having an isocyanate group at the terminal is produced, and if necessary, After neutralizing a part or all of hydrophilic groups such as anionic groups of the urethane prepolymer (A ′), mixing with an aqueous medium (C), and using the chain extender as necessary By extending the chain, a urethane resin (A) aqueous dispersion in which the urethane resin (A) is dispersed or dissolved in the aqueous medium (C) can be obtained.
- the reaction between the polyisocyanate (a1) and the polyol (a2) is, for example, an equivalent ratio of the isocyanate group [X] of the polyisocyanate (a1) and the hydroxyl group [Y] of the polyol (a2) [isocyanate group. It is preferable to carry out in the range where [X] / hydroxyl group [Y]] is 0.90 to 2.0.
- an organic solvent can also be used as a solvent as described above.
- the organic solvent include ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran and dioxane; acetic esters such as ethyl acetate and butyl acetate; nitriles such as acetonitrile; amides such as dimethylformamide and N-methylpyrrolidone.
- the organic solvent is preferably removed by distillation or the like after the urethane resin (A) or composite resin particle (D) is produced.
- the urethane resin (A) obtained by the above method has a printed material excellent in adhesion and printability, a conductive pattern excellent in fine line property and durability, etc. Those having a weight average molecular weight are preferably used, and those having a weight average molecular weight of 20,000 to 100,000 are more preferably used.
- the urethane resin (A) obtained by the above method may have various functional groups as necessary.
- the functional group include crosslinks such as alkoxysilyl groups, silanol groups, hydroxyl groups, and amino groups. Sex functional group.
- the alkoxysilyl group or silanol group can be introduced into the polyurethane (A) by using ⁇ -aminopropyltriethoxysilane or the like when the urethane resin (A) is produced.
- crosslinkable functional group those which form a crosslink structure by reacting with the crosslinkable functional groups or the crosslinker (E) described later by heating to approximately 100 ° C or higher, preferably 120 ° C or higher are used. be able to.
- the receptor layer-forming resin composition containing the same is used.
- the receiving layer constituting the receiving substrate obtained by applying to the substrate and drying or the like does not substantially form a crosslinked structure.
- a crosslinking reaction can be formed by heating or the like to form a crosslinked structure.
- the functional group capable of undergoing a crosslinking reaction by heating to 100 ° C. or higher, preferably 120 ° C. or higher, depends on the selection of the crosslinking agent (E) to be used in combination.
- a crosslinking agent such as a blocked isocyanate compound is used.
- a hydroxyl group or an amino group can be used.
- the crosslinkable functional group is preferably contained in a total range of 0.005 equivalent / kg to 1.5 equivalent / kg with respect to the total amount of the urethane resin (A).
- the vinyl polymer (B) it is preferable to use a polymer having a glass transition temperature of 10 ° C. to 70 ° C. in order to form a printed matter excellent in printability, particularly fine line property.
- the glass transition temperature of the said vinyl polymer (B) is a value determined by calculation mainly based on the composition of the vinyl monomer used for manufacture of this vinyl polymer (B).
- the vinyl polymer having the predetermined glass transition temperature can be obtained by using a combination of vinyl monomers described later.
- the receptor layer-forming resin composition has a good film-forming property, and when the receptor substrate is wound around a roll or the like, the receptor layer is laminated.
- a glass transition temperature of 10 ° C. to 40 ° C. from the viewpoint of providing a level of blocking resistance that does not cause sticking with time on the back surface of the support constituting the receiving substrate. preferable.
- the vinyl polymer (B) preferably has a weight average molecular weight of 800,000 or more, and has a weight average of 1,000,000 or more in order to form a printed matter having no bleeding and excellent printability. It is more preferable to use one having a molecular weight. The same applies to the formation of a receiving layer of a fluid such as a conductive ink that is free from bleeding and has excellent thin-line properties.
- the upper limit of the weight average molecular weight of the vinyl polymer (B) is not particularly limited, but is preferably about 10 million or less, more preferably 5 million or less.
- the vinyl polymer (B) may have various functional groups as required.
- the functional group include an amide group, a hydroxyl group, a glycidyl group, an amino group, a silyl group, and an aziridinyl group.
- Crosslinkable functional groups such as isocyanate group, oxazoline group, cyclopentenyl group, allyl group, carboxyl group, and acetoacetyl group.
- the crosslinkable functional group forms a cross-linked structure by printing on the receiving base material using a fluid such as ink, followed by a cross-linking reaction by heating or the like.
- a fluid such as ink
- a printed matter such as a conductive pattern can be formed.
- crosslinkable functional group for example, it is preferable to use one that can form a crosslinked structure by heating to approximately 100 ° C. or higher, preferably 120 ° C. or higher, specifically, methylol. It is preferable to use one or more thermally crosslinkable functional groups selected from the group consisting of amide groups and alkoxymethylamide groups.
- alkoxymethylamide group examples include an amide group formed by bonding a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, a butoxymethyl group or the like to a nitrogen atom.
- crosslinkable functional group for example, a hydroxyl group or a carboxyl group is preferably used when a crosslinking agent (E) described later is used.
- An amino group can also be used when the conditions for forming the receptor layer can be sufficiently controlled.
- the vinyl polymer (B) among those described above, it is preferable to use a polymer having at least one selected from the group consisting of a methylolamide group and an alkoxymethylamide group, and the durability of the receiving layer and various supports. It is particularly preferable for greatly improving the adhesion to the body.
- vinyl polymer (B) various types can be used.
- a polymer obtained by radical polymerization of a conventionally known vinyl monomer can be used.
- vinyl monomers that can be used in the production of the vinyl polymer (B) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, and (meth) acrylic acid.
- methyl methacrylate is a fine line having a width of about 0.01 ⁇ m to 200 ⁇ m, preferably about 0.01 ⁇ m to 150 ⁇ m, which is required when forming a conductive pattern such as an electronic circuit. It is preferable to use it in order to enable printing (improvement of fine line properties) without causing it.
- the methyl methacrylate is used for imparting excellent adhesion between the receptor layer and the support, regardless of the influence of heat or the like in the baking step when the conductive pattern is produced. Is preferred.
- vinyl monomers that can be used in producing the vinyl polymer (B) include acrylic acid, methacrylic acid, ⁇ -carboxyethyl (meth) acrylate, 2- (meth) Carboxyl groups such as acryloylpropionic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, itaconic acid half ester, maleic acid half ester, maleic anhydride, itaconic anhydride, ⁇ - (meth) acryloyloxyethyl hydrogen succinate, etc.
- the vinyl monomer can be used.
- the vinyl monomer having a carboxyl group may be neutralized with ammonia, potassium hydroxide, or the like.
- Examples of the other vinyl monomer include one or more amide groups selected from the group consisting of a methylolamide group and an alkoxymethylamide group, an amide group other than the above, and a hydroxyl group in the vinyl polymer (B).
- the crosslinkable functional group such as glycidyl group, amino group, silyl group, aziridinyl group, isocyanate group, oxazoline group, cyclopentenyl group, allyl group, carbonyl group, acetoacetyl group, etc.
- the vinyl monomer can be used.
- Examples of the vinyl monomer having at least one amide group selected from the group consisting of a methylolamide group and an alkoxymethylamide group that can be used for the crosslinkable functional group-containing vinyl monomer include N-methylol (meth). Acrylamide, N-methoxymethyl (meth) acrylamide, N-methoxyethoxymethyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, N-propoxymethyl (meth) acrylamide, N-isopropoxymethyl (meth) acrylamide, N -N-butoxymethyl (meth) acrylamide, N-isobutoxymethyl (meth) acrylamide, N-pentoxymethyl (meth) acrylamide, N-ethoxymethyl-N-methoxymethyl (meth) acrylamide, N, N'-dimethylol (Meta) Acry Amides, N-ethoxymethyl-N-propoxymethyl (meth) acrylamide, N, N′-dipropoxymethyl
- Nn-butoxymethyl (meth) acrylamide and N-isobutoxymethyl (meth) acrylamide are used for printed matter with excellent printability and durability, and conductivity with excellent fineness and durability. It is preferable for obtaining a pattern or the like.
- vinyl monomer having a crosslinkable functional group examples include those other than those described above, for example, an amide group-containing vinyl monomer such as (meth) acrylamide, 2-hydroxyethyl (meth) acrylate, and (meth) acrylic.
- an amide group-containing vinyl monomer such as (meth) acrylamide, 2-hydroxyethyl (meth) acrylate, and (meth) acrylic.
- Polymerizable monomer having a glycidyl group (meth) acrylic acid Polymerizable monomers having an amino group such as noethyl, dimethylaminoethyl (meth) acrylate, N-monoalkylaminoalkyl (meth) acrylate, N, N-dialkylaminoalkyl (meth) acrylate; vinyltrichlorosilane , Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris ( ⁇ -methoxyethoxy) silane, ⁇ - (meth) acryloxypropyltrimethoxysilane, ⁇ - (meth) acryloxypropyltriethoxysilane, ⁇ - (meth) acryl Roxypropylmethyldimethoxysilane, ⁇ - (meth) acryloxypropylmethyldiethoxysilane, ⁇ - (meth) acryloxypropyltriisopropoxysilane, N- ⁇ - (
- the vinyl monomers include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl versatate, methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, amyl vinyl ether, hexyl vinyl ether, ( (Meth) acrylonitrile, styrene, ⁇ -methylstyrene, vinyltoluene, vinylanisole, ⁇ -halostyrene, vinylnaphthalene, divinylstyrene, isoprene, chloroprene, butadiene, ethylene, tetrafluoroethylene, vinylidene fluoride, N-vinylpyrrolidone, polyethylene Glycol mono (meth) acrylate, glycerol mono (meth) acrylate, vinyl sulfonic acid, styrene sulfonic acid, allyl sulfonic acid,
- N-butoxymethyl (meth) acrylamide and N-isobutoxymethyl (meth) acrylamide which can undergo a self-crosslinking reaction by heating or the like are used alone or in combination.
- (meth) acrylamide and a hydroxyl group-containing vinyl monomer such as 2-hydroxyethyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate are preferably used in combination.
- a functional group that can be a crosslinking point with the crosslinking agent (E), such as a hydroxyl group, is introduced to introduce 2-hydroxyethyl (meth) acrylate, ( More preferably, 2-hydroxypropyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate are used.
- the use of the vinyl monomer having a hydroxyl group is preferable when an isocyanate crosslinking agent is used as the crosslinking agent (E) described later.
- the vinyl monomer having a crosslinkable functional group can be used in the range of 0% by mass to 50% by mass with respect to the total amount of the vinyl monomer mixture.
- the crosslinking agent (E) undergoes a self-crosslinking reaction, or when the crosslinking agent (E) reacts with a crosslinkable functional group that the urethane resin (A) can have, the crosslinkable functional group. It is not necessary to use a vinyl monomer having
- the vinyl monomer having the amide group is based on the total amount of the vinyl monomer mixture when introducing a self-crosslinking reactive methylolamide group or the like. It is preferably used in the range of 0.1% by mass to 50% by mass, and more preferably in the range of 1% by mass to 30% by mass.
- the vinyl monomer having another amide group used in combination with the self-crosslinking reactive methylolamide group or the vinyl monomer having a hydroxyl group is 0.1% based on the total amount of the vinyl monomer. It is preferably used in the range of mass% to 30 mass%, more preferably in the range of 1 mass% to 20 mass%.
- the vinyl monomer having a hydroxyl group depends on the type of the crosslinking agent (E) used in combination, but the total amount of the vinyl monomer mixture. In general, it is preferably used in the range of 0.05% by mass to 50% by mass, more preferably in the range of 0.05% by mass to 30% by mass, and 0.1% by mass to 10% by mass. More preferably it is used.
- the (meth) acrylic acid alkyl ester is preferably used in the range of 30% by mass to 95% by mass with respect to the total amount of the vinyl monomer mixture used for the production of the vinyl polymer (B).
- methyl (meth) acrylate is preferably used in an amount of 10% to 70% by weight, more preferably 30% to 65% by weight, based on the total amount of the vinyl monomer mixture
- An alkyl acrylate having an alkyl group having 2 to 12 carbon atoms, preferably an alkyl acrylate having an alkyl group having 3 to 8 carbon atoms, more preferably butyl (meth) acrylate is 10 It is used in the range of mass% to 50 mass%.
- the vinyl polymer (B) can be produced by polymerizing a mixture of various vinyl monomers as described above by a conventionally known method, and has excellent printability and fine lineability without blurring. It is preferable to apply an emulsion polymerization method as a means for obtaining a high molecular weight polymer capable of forming a receiving layer capable of forming a printed matter.
- emulsion polymerization method for example, water, a vinyl monomer mixture, a polymerization initiator, and, if necessary, a chain transfer agent, an emulsifier, a dispersion stabilizer, and the like are collectively supplied and mixed in a reaction vessel.
- a polymerization method, a monomer dropping method in which a vinyl monomer mixture is dropped into a reaction vessel and polymerization, or a vinyl monomer mixture, an emulsifier, etc. and water mixed in advance are dropped into the reaction vessel for polymerization.
- a pre-emulsion method or the like can be applied.
- the temperature during the emulsion polymerization varies depending on the type of vinyl monomer and polymerization initiator used, but is preferably about 30 to 90 ° C., for example, and the polymerization time is preferably about 1 to 10 hours, for example.
- polymerization initiator examples include persulfates such as potassium persulfate, sodium persulfate, and ammonium persulfate, organic peroxides such as benzoyl peroxide, cumene hydroperoxide, and t-butyl hydroperoxide, and peroxides.
- emulsifiers that can be used for the production of the vinyl polymer (B) include anionic surfactants, nonionic surfactants, 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.
- emulsifier in addition to the above-mentioned surfactants, fluorine-based surfactants, silicone-based surfactants, and emulsifiers having a polymerizable unsaturated group generally called “reactive emulsifier” in the molecule Can also be used.
- Examples of the reactive emulsifier include “Latemul S-180” (manufactured by Kao Corporation) having a sulfonic acid group and a salt thereof, “Eleminol JS-2, RS-30” (manufactured by Sanyo Chemical Industries, Ltd.) and the like; “Aqualon HS-10, HS-20, KH-1025” (Daiichi Kogyo Seiyaku Co., Ltd.), “Adekaria Soap SE-10, SE-20” (Asahi Denka Kogyo Co., Ltd.) having sulfate groups and salts thereof “New Frontier A-229E” having a phosphate group (Daiichi Kogyo Seiyaku Co., Ltd.), etc .; “Aqualon RN-10, RN-20, RN-30, RN-50 having a nonionic hydrophilic group” (Daiichi Kogyo Seiyaku Co., Ltd.) can be used.
- aqueous medium used for manufacture of the said vinyl polymer (B) the thing similar to what was illustrated as an aqueous medium (C) mentioned later can be used.
- lauryl mercaptan can be used, and 0% by mass to 1.0% by mass with respect to the total amount of the vinyl monomer mixture. %, Preferably in the range of 0% to 0.5% by weight.
- the resin composition for forming a receiving layer in which the urethane resin (A) and the vinyl polymer (B) are independently present in the aqueous medium (C) is, for example, an aqueous dispersion of the urethane resin (A) obtained above. It can manufacture by mixing a body and the aqueous dispersion of the said vinyl polymer (B).
- the receiving layer forming resin composition containing the composite resin particles (D) formed by the urethane resin (A) and the vinyl polymer (B) can be produced, for example, by the following method.
- the composite resin particle (D) is obtained by reacting the polyisocyanate (a1), the polyol (a2) and, if necessary, a chain extender and dispersing in water to thereby form a urethane resin (A).
- the water dispersion can be produced by a step (W) for producing an aqueous dispersion, and a step (Y) for producing a vinyl polymer (B) by polymerizing the vinyl monomer in the aqueous dispersion.
- the urethane resin (A) is obtained by reacting the polyisocyanate (a1) with the polyol (a2) in the absence of a solvent or in an organic solvent or in the presence of a reactive diluent such as a vinyl monomer. Next, a part or all of the hydrophilic group of the urethane resin (A) is neutralized with a basic compound or the like as necessary, and further reacted with a chain extender as necessary. Then, an aqueous dispersion of the urethane resin (A) is produced by dispersing it in the aqueous medium (D).
- the vinyl monomer is supplied into the aqueous dispersion of the urethane resin (A) obtained above, and the vinyl monomer is radically polymerized in the urethane resin (A) particles to give a vinyl polymer (B ).
- a resin composition for forming a receiving layer in which the composite resin particles (D) in which the vinyl polymer (B) is contained in the urethane resin (A) particles is dispersed in an aqueous medium (C) can be produced. it can.
- the urethane resin (A) has a high viscosity and is not excellent in workability
- the usual resin such as methyl ethyl ketone, N-methylpyrrolidone, acetone, dipropylene glycol dimethyl ether, etc.
- Organic solvents and reactive diluents can be used.
- the use of a vinyl monomer that can be used for the production of the vinyl polymer (B) as the reactive diluent improves the production efficiency of the resin composition for forming the receiving layer by omitting the solvent removal step. It is preferable when aiming at.
- Examples of the aqueous medium (C) in which the urethane resin (A), the vinyl polymer (B), or the composite resin particles (D) obtained by the above reaction can be dispersed or dissolved include water and organic solvents miscible with water. And mixtures thereof.
- Examples of 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 ether of polyalkylene glycol And lactams such as N-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.
- water alone or a mixture of water and an organic solvent miscible with water is preferable, and only water is particularly preferable.
- the aqueous medium (C) is preferably contained in an amount of 50% by mass to 90% by mass, and more preferably 65% by mass to 85% by mass with respect to the total amount of the resin composition for forming a receiving layer.
- the resin composition for forming a receiving layer of the present invention in order to further improve the printability and fine lineability when using a fluid such as an aqueous pigment ink, a conductive ink, or a plating nucleating agent, A combination of water-soluble resins can be used.
- water-soluble resin examples include polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl acetal, polyalkylene oxide, starch, methylcellulose, hydroxycellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, carboxymethylcellulose and other cellulose derivatives, polyethyleneimine, polyamide, various Quaternary ammonium base-containing water-soluble resins, modified products thereof, and the like can be used. Among these, it is preferable to use polyvinyl alcohol.
- the resin composition for forming a receiving layer of the present invention includes a crosslinking agent (E), a pH adjuster, a film-forming aid, a leveling agent, a thickening agent as necessary, as long as the effects of the present invention are not impaired. You may use it, adding a well-known thing suitably, such as an agent, a water repellent, and an antifoamer.
- crosslinking agent (E) examples include a metal chelate compound, a polyamine compound, an aziridine compound, a metal salt compound, and an isocyanate compound that can react at a relatively low temperature of approximately 25 ° C. to less than 100 ° C. to form a crosslinked structure. It reacts at a relatively high temperature of about 100 ° C. or higher, such as one or more selected from the group consisting of a crosslinking agent (e1-1), a melamine compound, an epoxy compound, an oxazoline compound, a carbodiimide compound, and a blocked isocyanate compound.
- a thermal crosslinking agent (e1-2) capable of forming a crosslinked structure and various photocrosslinking agents can be used.
- a resin composition for forming a receiving layer containing the thermal crosslinking agent (e1-1) for example, it is applied to the surface of a support, dried at a relatively low temperature, and then printed using the fluid. After that, by forming a cross-linked structure by heating to a temperature of less than 100 ° C., it has excellent durability with a level that can prevent the loss of conductive substances and pigments regardless of the influence of heat and external force over a long period of time. An ink-receiving substrate having properties can be formed.
- the resin composition for forming a receiving layer contains the thermal crosslinking agent (e1-2), for example, it is applied to the surface of the support and dried at a low temperature of from room temperature (25 ° C.) to less than about 100 ° C. Then, after manufacturing an ink receiving substrate that does not form a cross-linked structure and then printing using ink or the like, the cross-linked structure is formed by heating at a temperature of, for example, 100 ° C. or higher, preferably 120 ° C. or higher. As a result, it is possible to obtain a printed matter or a conductive pattern having exceptionally excellent durability that does not cause ink peeling or the like regardless of the influence of heat, external force, or the like over a long period of time.
- the thermal crosslinking agent (e1-2) for example, it is applied to the surface of the support and dried at a low temperature of from room temperature (25 ° C.) to less than about 100 ° C. Then, after manufacturing an ink receiving substrate that does not form a cross-linked structure and
- Examples of the metal chelate compound that can be used in the thermal crosslinking agent (e1-1) include acetylacetone, which is a polyvalent metal such as aluminum, iron, copper, zinc, tin, titanium, nickel, antimony, magnesium, vanadium, chromium, and zirconium. Coordination compounds, acetoacetate coordination compounds and the like can be used, and it is preferable to use acetylacetone aluminum which is an acetylacetone coordination compound of aluminum.
- a polyamine compound that can be used for the thermal crosslinking agent (e1-1) for example, a tertiary amine such as triethylamine, triethylenediamine, dimethylethanolamine or the like can be used.
- aziridine compound that can be used in the thermal crosslinking agent (e1-1) examples include 2,2-bishydroxymethylbutanol-tris [3- (1-aziridinyl) propionate], 1,6-hexamethylenediethylene urea. Diphenylmethane-bis-4,4′-N, N′-diethyleneurea and the like can be used.
- Examples of the metal salt compound that can be used as the crosslinking agent (e1-1) include aluminum sulfate, aluminum alum, aluminum sulfite, aluminum thiosulfate, polyaluminum chloride, aluminum nitrate nonahydrate, and aluminum chloride hexahydrate.
- Water-soluble metal salts such as aluminum-containing compounds such as titanium tetrachloride, tetraisopropyl titanate, titanium acetylacetonate, and titanium lactate can be used.
- isocyanate compounds that can be used in the thermal crosslinking agent (e1-1) include tolylene diisocyanate, hydrogenated tolylene diisocyanate, triphenylmethane triisocyanate, methylene bis (4-phenylmethane) triisocyanate, isophorone diisocyanate, hexamethylene.
- a polyisocyanate such as diisocyanate and xylylene diisocyanate, an isocyanurate type polyisocyanate compound obtained by using them, an adduct comprising them and trimethylolpropane, the polyisocyanate compound and a polyol such as trimethylolpropane.
- Polyisocyanate group-containing urethane obtained by reacting can be used.
- hexamethylene diisocyanate nurate adduct of hexamethylene diisocyanate and trimethylolpropane
- adduct of tolylene diisocyanate and trimethylol propane adduct of xylylene diisocyanate and trimethylol propane, etc. are used. It is preferable.
- Examples of the melamine compound that can be used in the thermal crosslinking agent (e1-2) include hexamethoxymethyl melamine, hexaethoxymethyl melamine, hexapropoxymethyl melamine, hexabutoxymethyl melamine, hexapentyloxymethyl melamine, and hexahexyl.
- Oxymethyl melamine or a mixed etherified melamine obtained by combining these two types can be used.
- trimethoxymethyl melamine and hexamethoxymethyl melamine are preferably used.
- becamine M-3, APM, J-101 (manufactured by DIC Corporation) and the like can be used.
- the melamine compound can form a crosslinked structure by a self-crosslinking reaction.
- a catalyst such as an organic amine salt may be used to promote the self-crosslinking reaction.
- catalyst ACX, 376 etc. can be used.
- the catalyst is preferably in the range of approximately 0.01% by mass to 10% by mass with respect to the total amount of the melamine compound.
- Examples of the epoxy compound that can be used for the thermal crosslinking agent (e1-2) include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, hexamethylene glycol diglycidyl ether, cyclohexanediol diglycidyl ether, and glycerin diglycidyl ether.
- Polyglycidyl ethers of aliphatic polyhydric alcohols such as glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether; polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polytetramethylene glycol diglycidyl ether
- Polyglycidyl ethers of polyalkylene glycols such as 1,3-bis (N, Polyglycidylamines such as' -diglycidylaminoethyl) cyclohexane; polyglycidyl esters of polycarboxylic acids [succinic acid, adipic acid, butanetricarboxylic acid, maleic acid, phthalic acid, terephthalic acid, isophthalic acid, benzenetricarboxylic acid, etc.] Bisphenol A-based
- polyglycidylamines such as 1,3-bis (N, N′-diglycidylaminoethyl) cyclohexane and polyglycidyl ethers of aliphatic polyhydric alcohols such as glycerin diglycidyl ether.
- Examples of the epoxy compound include ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropyltriethoxysilane, ⁇ -glycidoxypropylmethyldimethoxysilane, and ⁇ -glycidoxypropyl other than those described above.
- a glycidyl group-containing silane compound such as ⁇ -glycidoxypropyltriisopropenyloxysilane can be used.
- Examples of the oxazoline compound that can be used in the thermal crosslinking agent (e1-2) include 2,2′-bis- (2-oxazoline), 2,2′-methylene-bis- (2-oxazoline), 2 , 2'-ethylene-bis- (2-oxazoline), 2,2'-trimethylene-bis- (2-oxazoline), 2,2'-tetramethylene-bis- (2-oxazoline), 2,2'- Hexamethylene-bis- (2-oxazoline), 2,2'-octamethylene-bis- (2-oxazoline), 2,2'-ethylene-bis- (4,4'-dimethyl-2-oxazoline), 2 , 2'-p-phenylene-bis- (2-oxazoline), 2,2'-m-phenylene-bis- (2-oxazoline), 2,2'-m-phenylene-bis- (4,4'- Dimethyl-2-oxa Phosphorus), bis - (2-oxazolinyl sulfony
- oxazoline compound for example, an oxazoline group-containing polymer obtained by polymerizing a combination of the following addition polymerizable oxazoline and other monomers as required may be used.
- Examples of the addition polymerizable oxazoline include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline. , 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-methyl-2-oxazoline, 2-isopropenyl-5-ethyl-2-oxazoline, etc., alone or in combination Can do. Of these, the use of 2-isopropenyl-2-oxazoline is preferred because it is easily available industrially.
- carbodiimide compounds that can be used for the thermal crosslinking agent (e1-2) include poly [phenylenebis (dimethylmethylene) carbodiimide] and poly (methyl-1,3-phenylenecarbodiimide).
- poly [phenylenebis (dimethylmethylene) carbodiimide] examples include poly [phenylenebis (dimethylmethylene) carbodiimide] and poly (methyl-1,3-phenylenecarbodiimide).
- Carbodilite V-01, V-02, V-03, V-04, V-05, V-06 Non-available products
- UCALINK XL-29SE XL-29MP (Union Carbide Co., Ltd.) Etc.
- the blocked isocyanate compound that can be used in the thermal crosslinking agent (e1-2) a part or all of the isocyanate groups of the isocyanate compound exemplified as the thermal crosslinking agent (e1-1) may be formed by a blocking agent. What was sealed can be used.
- the blocking agent examples include phenol, cresol, 2-hydroxypyridine, butyl cellosolve, propylene glycol monomethyl ether, benzyl alcohol, methanol, ethanol, n-butanol, isobutanol, dimethyl malonate, diethyl malonate, methyl acetoacetate, Ethyl acetoacetate, acetylacetone, butyl mercaptan, dodecyl mercaptan, acetanilide, acetic acid amide, ⁇ -caprolactam, ⁇ -valerolactam, ⁇ -butyrolactam, succinimide, maleic imide, imidazole, 2-methylimidazole, urea, thiourea, Ethyleneurea, formamide oxime, acetaldoxime, acetone oxime, methyl ethyl ketoxime, methyl isobutyl ketoxime, cyclohexa N'okishimu,
- Elastolon BN-69 (Daiichi Kogyo Seiyaku Co., Ltd.) or the like can be used as a water-dispersed commercial product.
- the (block) isocyanate compound, the melamine compound, the oxazoline compound, and the carbodiimide compound as a crosslinking agent, and use a vinyl resin having a hydroxyl group or a carboxyl group as the vinyl resin (A).
- the said crosslinking agent (E) changes with kinds etc., it is 0. 0 normally with respect to 100 mass parts of total mass of the said urethane resin (A), the said vinyl polymer (B), and the said composite resin particle (D). It is preferably used in the range of 01% by mass to 60% by mass, more preferably in the range of 0.1% by mass to 10% by mass, and in the range of 0.1% by mass to 5% by mass. However, it is preferable for forming a receiving layer capable of forming a printed image having excellent printability. In addition, even when forming a conductive pattern using conductive ink or the like, the level that can be used to realize higher density of electronic circuits or the like without causing bleeding of printed portions such as fine lines is much better. It is preferable because it can provide fine lineability and can further improve the adhesion between the receptor layer and the support.
- the crosslinking agent (E) is preferably added and used before coating or impregnating the support layer-forming resin composition of the present invention on the support surface.
- thermosetting resins such as phenol resins, urea resins, melamine resins, polyester resins, A polyamide resin, a urethane resin, or the like can be mixed and used.
- the additive 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 receiving layer forming resin composition of the present invention. It is more preferable.
- the amount of the additive used is not particularly limited as long as the effect of the present invention is not impaired, but is 0.01% by mass to 40% by mass with respect to the total amount of solids in the resin composition for forming a conductive receiving layer. % Is preferable.
- the receptor layer that can be formed using the resin composition for forming the receptor layer is composed of a urethane resin (A), a vinyl polymer (B), and composite resin particles (D) constituting the receptor layer in a fluid such as ink. It is a swellable type that can be accurately fixed to the surface of the ink receiving layer by dissolving a suitable amount of the solvent and absorbing the solvent to absorb the solvent. Therefore, it is possible to obtain a printed matter such as a conductive pattern without bleeding.
- the resin 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 resin composition on part or all of the surface 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 coated with the receiving substrate on one or both sides of the support, or, when the support is a fiber substrate or the like, impregnated in the support to form the receiving layer. It can manufacture by volatilizing the aqueous medium (C) contained in a resin composition.
- the support examples include fine paper, coated paper, polyimide resin, polyamideimide resin, polyamide resin, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, acrylonitrile-butadiene-styrene (ABS), and poly (meth) acrylic.
- a support made of acrylic resin such as methyl acid, polyvinylidene fluoride, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyethylene, polypropylene, polyurethane, cellulose nanofiber, silicon, ceramics, glass, etc.
- a support made of a metal such as a support, 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 for coating or impregnating the receptor layer-forming resin composition on the support known and conventional methods can be used, for example, gravure method, coating method, screen method, roller method, rotary method, A spray method or the like can be applied.
- the method for volatilizing the aqueous medium (C) contained in the receptor layer after coating or impregnating the receptor layer-forming resin composition of the present invention on the support is not particularly limited. However, for example, a method of drying using a dryer is common.
- the drying temperature may be set to a temperature that can volatilize the aqueous medium (C) and does not adversely affect the support.
- a method for removing a solvent such as a solvent that may be contained in the resin composition after coating or impregnating the support layer-forming resin composition of the present invention to a part or all of the support surface Although not limited, for example, 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 thermal crosslinking agent (e1-1) when used, it is preferably dried at a temperature of approximately 25 ° C. to less than 100 ° C., and when the thermal crosslinking agent (e1-2) is used. Is preferably about 100 ° C. or higher, preferably about 120 ° C. to 300 ° C.
- the temperature is from room temperature (25 ° C.) to about 100 ° C. It is preferable to adjust so that it is dried at a relatively low temperature and does not form a crosslinked structure before printing.
- the amount of the resin composition for forming the receiving layer on the support is 3 to 60 g based on the area of the support from the viewpoint of maintaining a very high level of color developability and maintaining good production efficiency.
- / M 2 is preferable, and 20 to 40 g / m 2 is particularly preferable in consideration of the absorbability of the solvent contained in the fluid and the production cost.
- the color developability of the obtained printed matter can be further improved.
- 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 for example, alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, ethyl carbitol, ethyl cellosolve, butyl cellosolve, and polar solvents such as N-methylpyrrolidone can be used.
- 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 weight, more preferably 1 to 10% by weight, 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.
- alcohols 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 examples 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 2-ethylhexyl acetate, dimethyl phthalate, diethyl phthalate, butyl lactate and the like.
- 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 base material (conductive ink receiving base material) of the present invention that can be used for forming the conductive pattern is similar to the above, and the resin composition for forming a receiving layer is formed on part or all of the surface of various supports. It has a receiving layer formed using a thing.
- 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 receiving resin composition for forming a receiving layer is coated and impregnated on a part or all of one side or both sides of a support, and then the resin composition for forming a conductive receiving layer is incorporated into the conductive receiving layer forming resin composition. It can manufacture by removing the aqueous medium (C) contained.
- 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 as a method of applying or impregnating the receptor layer-forming resin composition to a part or the whole of the support surface.
- a gravure method a coating method, a screen method, A roller method, a rotary method, a spray method, an ink jet method, or the like can be applied.
- a method of removing the aqueous medium (C) that can be contained in the resin composition after coating or impregnating part or all of the surface of the support with the resin composition for forming a receiving layer of the present invention Although not particularly limited, for example, 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 resin composition for forming the receiving layer on the surface of the support is determined by taking into consideration the amount of the solvent contained in the fluid such as conductive ink, the thickness of the conductive pattern, etc.
- the solid content of the resin is preferably in the range of 0.01 g / m 2 to 20 g / m 2 , and 0.01 g / m 2 to 10 g / m 2 considering the absorbability of the solvent in the fluid and the production cost. m 2 is particularly preferred.
- the fine-line property of a receiving base material can be improved further by making the adhesion amount of the said resin composition for receiving layer formation to the support body surface increase.
- the texture of the receiving base material tends to become slightly hard.
- the thickness relatively thin at about m 2 to 10 g / m 2 .
- 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.
- 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 in preventing
- 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 resin composition for forming a receiving layer of the present invention is particularly preferably used in combination with a conductive ink containing a polar solvent
- the nonpolar solvent is 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 in.
- the same medium as the aqueous medium (C) can be used.
- the same medium as the aqueous medium (C) can be used.
- water may be used, or water and a 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 printed by the above-described method on the receiving substrate by closely contacting and joining the conductive substances contained in the conductive ink.
- Examples of the method for bonding the conductive substances include a heat baking method and a light irradiation method.
- the firing is preferably performed in the range of approximately 80 ° C. to 300 ° C. for approximately 2 minutes to 200 minutes.
- the calcination may be performed in the air, but part or all of the calcination step may be performed in a reducing atmosphere from the viewpoint of preventing oxidation of the metal.
- 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 cross-linking agent (e1-2) when used and a cross-linked structure is to be formed after printing using a conductive ink or the like, the cross-linked structure is formed after printing through the firing step. Is done. Thereby, durability of printed matter, such as a conductive pattern, can be improved to each step.
- the heating temperature varies depending on the type of the cross-linking agent (E) used, the combination of cross-linkable functional groups, and the like, but is generally in the range of 80 ° C. to 300 ° C. It is preferably 100 ° C. to 300 ° C., more 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 receiving layer formed using the receiving layer forming resin composition, and the surface of the receiving layer is formed.
- a plating nucleus is supported on a part or all of the coating nucleus by applying a plating nucleus agent, and after passing through a baking step or the like as necessary, further after electrolytic plating treatment, electroless plating treatment, or after the electroless plating treatment What has a plating film formed by performing an electroplating 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 10 nm to 1 ⁇ m.
- the same solvents as those exemplified as the solvent such as an aqueous medium and 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
- aminopolyesters such as iminodiacetic acid, nitrilotriacetic acid, ethylenediaminediacetic acid, ethylenediaminetetraacetic acid
- It may contain a complexing agent 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 in manufacturing an electromagnetic wave shield wiring of a plasma display, more specifically, a circuit board.
- 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 board
- TAB automatic tape bonding
- COF chip-on-film
- PWB printed wiring board
- aqueous dispersion of mass% urethane resin (A) -1 was obtained.
- the urethane resin (A) -1 obtained here had an acid value of 30, an aliphatic cyclic structure content calculated from the ratio of charged raw materials, 4452 mmol / kg, and a weight average molecular weight of 53,000.
- aqueous dispersion of mass% urethane resin (a1) -2 was obtained.
- the urethane resin (A) -2 obtained here had an acid value of 30, an aliphatic cyclic structure content calculated from the ratio of charged raw materials, 2714 mmol / kg, and a weight average molecular weight of 51,000.
- Polyester polyol obtained by reacting pentyl glycol and adipic acid, aliphatic cyclic structure content in the polyester polyol: 1426 mmol / kg, hydroxyl group equivalent 1000 g / equivalent), 2,2-dimethylolpropionic acid 6 parts by mass, 1,4-cyclohexanedimethanol 21.7 parts by mass, dicyclohexylmethane diisocyanate 106.2 parts by mass in a mixed solvent with methyl ethyl ketone 178 parts by mass, thereby having a urethane having an isocyanate group at the molecular end An organic solvent solution of the prepolymer was obtained.
- aqueous dispersion of mass% urethane resin (a1) -3 was obtained.
- the urethane resin (a1) -3 obtained here had an acid value of 30, an aliphatic cyclic structure content calculated from the ratio of charged raw materials, 4307 mmol / kg, and a weight average molecular weight of 88,000.
- ⁇ -aminopropyltriethoxysilane 12.5 parts by mass is mixed with the organic solvent solution of the urethane prepolymer, and the urethane prepolymer and ⁇ -aminopropyltriethoxysilane are reacted to form an aliphatic ring.
- An organic solvent solution of a urethane resin having a formula structure, a carboxyl group, and a hydrolyzable silyl group or silanol group was obtained.
- urethane resin (A) -4 17 parts by mass of a 25% by mass aqueous ethylenediamine solution is added to the aqueous dispersion, and the resulting polyurethane resin is chain-extended by stirring, followed by aging and desolvation, thereby solid content concentration of 30% by mass.
- An aqueous dispersion of urethane resin (A) -4 was obtained.
- the urethane resin (A) -4 obtained here had an acid value of 25, an aliphatic cyclic structure content calculated from the raw material ratio of 3921 mmol / kg, and a weight average molecular weight of 99000.
- a polycarbonate diol containing an aliphatic cyclic structure obtained by reaction, an aliphatic cyclic structure content in the polycarbonate polyol of 3000 mmol / kg, a hydroxyl group equivalent of 1000 g / equivalent) is 100 parts by mass, and 2,2-dimethylol
- propionic acid 9.7 parts by mass of propionic acid, 5.5 parts by mass of 1,4-cyclohexanedimethanol, and 51.4 parts by mass of dicyclohexylmethane diisocyanate in a mixed solvent of 111 parts by mass of methyl ethyl ketone, an isocyanate group is formed at the molecular terminal. Obtained an organic solvent solution of urethane prepolymer having .
- aqueous dispersion of mass% urethane resin (A) -5 was obtained.
- the urethane resin (A) -5 obtained here had an acid value of 24, an aliphatic cyclic structure content calculated from the raw material ratio of 4356 mmol / kg, and a weight average molecular weight of 61,000.
- aqueous dispersion of mass% urethane resin (A) ′-1 was obtained.
- the urethane resin (A) ′-1 obtained here had an acid value of 22, an aliphatic cyclic structure content calculated from the ratio of charged raw materials, 1172 mmol / kg, and a weight average molecular weight of 97,000.
- urethane resin (A) ′-2 34.4 parts by mass of a 25% by mass ethylenediamine aqueous solution is added to the aqueous dispersion and stirred to chain-extend the particulate polyurethane resin, and then aged and desolventized to obtain a solid content concentration of 30.
- An aqueous dispersion of mass% urethane resin (A) ′-2 was obtained.
- the urethane resin (A) ′-2 obtained here had an acid value of 30, an aliphatic cyclic structure content calculated from the ratio of charged raw materials, 5984 mmol / kg, and a weight average molecular weight of 70000.
- a vinyl monomer mixture comprising 60.0 parts by weight of methyl methacrylate, 38.0 parts by weight of n-butyl acrylate, and 2.0 parts by weight of methacrylic acid in a reaction vessel, and Aqualon KH-1025 ( Daiichi Kogyo Seiyaku Co., Ltd .: active ingredient 25% by mass)
- 0.1 parts by mass of potassium sulfate was added, and polymerization was performed for 60 minutes while maintaining the temperature in the reaction vessel at 75 ° C.
- the remaining monomer pre-emulsion 114 parts by mass
- 30 parts by mass of an aqueous solution of potassium persulfate active ingredient 1.0% by mass
- the temperature in the reaction vessel was cooled to 40 ° C., and aqueous ammonia (active ingredient 10% by mass) was used so that the pH of the aqueous dispersion in the reaction vessel was 8.5.
- deionized water was used so that the nonvolatile content was 20.0% by mass, followed by filtration through a 200 mesh filter cloth to obtain an aqueous dispersion of vinyl polymer (B) -1.
- Example 1 Preparation of Receptive Layer Forming Resin Composition (I-1) and Production of Receptive Substrate (II-1) Using It>
- the aqueous dispersion of urethane resin (A) -1 obtained above and the aqueous dispersion of -1 of vinyl polymer (B) were combined with the aqueous dispersion of urethane resin (A) -1: vinyl polymer (B-1 )
- Water dispersion 100: 350 (solid content mass ratio 30:70), and after using deionized water so that the non-volatile content is 20% by mass, by filtering through a 200 mesh filter cloth, A resin composition (I-1) for forming a receiving layer used in the present invention was obtained.
- the resin composition for forming a receiving layer (I-1) was applied to the surfaces of three types of supports shown in (i) to (iii) below so that the dry film thickness was 3 ⁇ m. It was coated and dried at 70 ° C. for 3 minutes using a hot air drier to obtain three types of receiving substrates (II-1) having a receiving layer formed on each support.
- Example 2 Preparation of Receptor Layer Forming Resin Composition (I-2) and Production of Receptive Substrate (II-2) Using It>
- the composite resin particles are constituted by the shell layer made of the urethane resin (A) -1 and the core layer made of the vinyl polymer (B) -2 by stirring at the same temperature for 60 minutes.
- An aqueous dispersion of (C) -1 was obtained.
- the reaction vessel is cooled to 40 ° C., then deionized water is used so that the non-volatile content becomes 20.0% by mass, and then filtered through a 200 mesh filter cloth.
- a resin composition for forming a receiving layer (I-2) was obtained.
- the resin composition for forming a receiving layer (I-2) obtained above was applied to the surface of three types of supports shown in (i) to (iii) below so that the dry film thickness was 3 ⁇ m. Each was coated using a hot air dryer and dried at 70 ° C. for 3 minutes using a hot air drier to obtain three types of receiving substrates (II-2) each having a receiving layer formed on each support.
- Examples 3 to 5 Preparation of Receptive Layer Forming Resin Compositions (I-3) to (I-5) and Production of Receiving Substrates (II-3) to (II-5) Using them>
- the type of urethane resin was changed to (A) -1 to (A) -3 shown in Table 1 below, and the composition of the vinyl monomer used in the production of the vinyl polymer was changed to the composition shown in Table 1 below.
- Resin compositions for forming a receiving layer (I-3) to (I-5) having a nonvolatile content of 20% by mass were prepared in the same manner as described in Example 2, except for changing to the above.
- the receiving layer forming resin compositions (I-3) to (I-5) obtained above were used in three types of supports shown in the following (i) to (iii) so that the dry film thickness was 3 ⁇ m.
- the surface of each substrate was coated with a bar coater and dried at 70 ° C. for 3 minutes using a hot air drier to obtain three types of receiving substrates (II) having an ink receiving layer formed on each support. -3) to (II-5) were obtained.
- the resin composition for forming a receiving layer (I-6) obtained above was applied to the surface of three types of supports shown in (i) to (iii) below so that the dry film thickness was 3 ⁇ m. Each was coated with a hot air dryer and dried at 70 ° C. for 3 minutes using a hot air dryer to obtain three types of ink receiving substrates (II-6) each having a receiving layer formed on each support. .
- Three types of supports shown in the following (i) to (iii) are prepared from the resin compositions for forming a receiving layer (I-7) to (I-11) obtained above so that the dry film thickness becomes 3 ⁇ m.
- Each of the substrates was coated with a bar coater and dried at 70 ° C. for 3 minutes using a hot air drier to obtain three types of receiving substrates (II ⁇ ) having a receiving layer formed on each support. 7) to (II-11) were obtained.
- Comparative Examples 1 and 2 Preparation of Receptor Layer Forming Resin Compositions (I′-1) to (I′-2) and Receiving Substrates (II′-1) to (II′-2) Using them Production>
- the type of urethane resin was changed to (A) '-1 to (A)'-2 shown in Table 1 below, and the composition of the vinyl monomer used for the production of the vinyl polymer was shown in Table 2 below.
- Resin compositions for forming a receiving layer (I′-1) to (I′-2) having a nonvolatile content of 20% by mass were prepared in the same manner as in Example 2 except that the composition was changed. .
- the receiving layer-forming resin compositions (I′-1) to (I′-2) obtained above were subjected to the following three types (i) to (iii) so that the dry film thickness was 3 ⁇ m.
- Three types of receiving substrates (each having a receiving layer formed on each support) were coated on the surface of the support using a bar coater and dried at 70 ° C. for 3 minutes using a hot air dryer. I'-1) to (I'-2) were obtained.
- the resin composition for forming the receiving layer (I′-3) was dried to a thickness of 3 ⁇ m. Each of these was coated and dried at 70 ° C. for 3 minutes using a hot air dryer to obtain three types of receiving substrates (II′-3) having an ink receiving layer formed on each support.
- Methyl methacrylate BA n-butyl acrylate
- NBMAM Nn-butoxymethyl acrylamide
- HEMA 2-hydroxyethyl methacrylate 4HBA
- MAA methacrylate cross-linked Agent 1; Melamine compound (DIC Corporation Becamine M-3, Trimethoxymethyl Melamine)
- a cellophane adhesive tape (manufactured by Nichiban Co., Ltd., CT405AP-24, 24 mm) is pressure-bonded to the surface (on the receiving layer) of each receiving substrate before printing, and then the cellophane adhesive tape is attached to the receiving substrate. Peeling in the direction of 90 degrees with respect to the surface. The adhesive surface of the peeled cellophane adhesive tape was visually observed, and the adhesiveness was evaluated based on the presence or absence of the adhering matter.
- the adhesive layer of the peeled cellophane adhesive tape was “A” in which no receptor layer was attached, and the receptor layer in a range of less than about 5% relative to the adhesive tape application area was peeled from the support,
- the adhesive layer attached to the adhesive tape is "B”.
- the adhesive layer in the range of about 5% to less than 50% of the adhesive tape is peeled off from the support, and the adhesive layer attached to the adhesive tape is "C”.
- About 50% or more of the receiving layer with respect to the affixing area was peeled off from the support and was attached to the adhesive tape as “D”.
- the printability of a print image obtained by printing using the solvent-based pigment ink was evaluated based on the following criteria.
- a print image formed using the above “total 400% of ink” was free from uneven color, bleeding, cracks, etc., and formed a uniform print image.
- [Ink preparation method] [Preparation of nano silver ink 1 for inkjet printing] Silver particles having an average particle diameter of 30 nm are dispersed in a mixed solvent composed of 65 parts by mass of diethylene glycol diethyl ether, 18 parts by mass of ⁇ -butyrolactone, 15 parts by mass of tetraethylene glycol dimethyl ether, and 2 parts by mass of tetraethylene glycol monobutyl ether. Thus, a nano-silver ink 1 for solvent-based inkjet printing was prepared.
- Nano silver ink 2 for solvent-based inkjet printing was prepared by dispersing silver particles having an average particle size of 30 nm in a solvent made of tetradodecane.
- Inkjet printers (Konica Minolta IJ Co., Ltd.) were applied to the surfaces of three types of receiving substrates obtained by using the supports (i), (ii) and (iii), respectively.
- a company inkjet tester EB100, evaluation printer head KM512L, discharge amount 42 pl) printing a straight line having a line width of 100 ⁇ m and a film thickness of 0.5 ⁇ m by about 1 cm, and then drying at 150 ° C. for 30 minutes.
- Printed matter (conductive pattern) was obtained.
- the receiving substrates described in Examples 4 to 6 and 8 to 11 were used, the printing was performed using the conductive ink, followed by a drying step for 30 minutes at 150 ° C.
- a cross-linked structure was formed in the layer. As shown in Tables 3 and 4, whether or not the crosslinked structure was formed was determined by “gel fraction of the conductive ink receiving layer formed by drying at room temperature (23 ° C.) and then heating at 70 ° C. And “the gel fraction of the conductive ink receiving layer formed by further heating at 150 ° C.”. That is, the gel fraction of the conductive ink receiving layer obtained by heating at 150 ° C. is compared with the gel fraction (uncrosslinked state) of the conductive ink receiving layer obtained by drying at room temperature and then heating at 70 ° C. Then, it was judged that the cross-linked structure was formed by heating at a high temperature when the amount increased by 25% by mass or more.
- the gel fraction of the receptor layer formed by drying at normal temperature (23 ° C.) and then heating at 70 ° C. was calculated by the following method.
- a resin composition for forming a receiving layer is poured onto a polypropylene film surrounded by cardboard so that the film thickness after drying becomes 100 ⁇ m, dried under conditions of a temperature of 23 ° C. and a humidity of 65% for 24 hours, and then 70 ° C.
- the receptor layer was formed by heat treatment for 3 minutes.
- the obtained receiving layer was peeled off from the polypropylene film and cut into a size of 3 cm in length and 3 cm in width to make a test piece. After measuring the mass (X) of the test piece 1, the test piece 1 was immersed in 50 ml of methyl ethyl ketone adjusted to 25 ° C. for 24 hours.
- the residue (insoluble matter) of the test piece 1 that did not dissolve in methyl ethyl ketone was filtered through a 300-mesh wire mesh by the immersion.
- the “gel fraction of the receiving layer formed by heating at 150 ° C.” was calculated by the following method.
- a resin composition for forming a receiving layer is poured onto a polypropylene film surrounded by cardboard so that the film thickness after drying is 100 ⁇ m, dried under conditions of a temperature of 23 ° C. and a humidity of 65% for 24 hours, and then 150 ° C.
- the receptor layer was formed by heating and drying for 30 minutes.
- the obtained receiving layer was peeled off from the polypropylene film and cut into a size of 3 cm in length and 3 cm in width to make a test piece 2. After measuring the mass (X ′) of the test piece 2, the test piece 2 was immersed in 50 ml of methyl ethyl ketone adjusted to 25 ° C. for 24 hours.
- the residue (insoluble matter) of the test piece 2 that was not dissolved in methyl ethyl ketone by the immersion was filtered through a 300-mesh wire mesh.
- the gel fraction was calculated based on the formula [(Y ′) / (X ′)] ⁇ 100.
- the screen printing silver paste was applied to the surfaces of three kinds of receiving substrates obtained using the supports (i), (ii) and (iii), respectively.
- a straight line having a width of 50 ⁇ m and a film thickness of 1 ⁇ m was printed by about 1 cm, and then dried at 150 ° C. for 30 minutes to obtain a printed matter (conductive pattern).
- the ink receiving layer has a cross-linked structure by performing a drying process for 30 minutes at 150 ° C. after printing using the ink. Been formed. The presence or absence of a crosslinked structure was determined by the same method as described above.
- the boundary between the non-printing portion and the non-printing portion is partially unclear, the entire line portion is smooth and usable level is “C”, which is about 1/3 of the outer edge portion of the printing portion (line portion). Bleeding can be confirmed in a range of about 1 ⁇ 2, and the boundary between the printed part and the non-printed part becomes partially unclear at that part, and the outer edge part and the middle part of the line part are unclear. “D” indicates that the part was not smooth, and bleeding was confirmed in a range of about 1 ⁇ 2 or more of the outer edge part of the printing part (line part), and the boundary between the printing part and the non-printing part was uniform in that part. What was unclear in the part and was not smooth between the outer edge part and the central part of the line part was evaluated as “E”.
- the nano silver ink 1 for inkjet printing was applied to the surface of two types of receiving substrates obtained using the supports (i) and (ii), respectively, and an inkjet printer (ink tester EB100 manufactured by Konica Minolta IJ Co., Ltd.).
- an inkjet printer ink tester EB100 manufactured by Konica Minolta IJ Co., Ltd.
- a printer head for evaluation KM512L and a discharge amount of 42 pl By using a printer head for evaluation KM512L and a discharge amount of 42 pl), a rectangular range (area) of 3 cm in length and 1 cm in width is printed with a film thickness of 0.5 ⁇ m and then dried at 150 ° C. for 30 minutes. , Printed matter (conductive pattern) was obtained.
- the ink receiving layer is subjected to a drying process for 30 minutes at 150 ° C. after printing using the ink. A crosslinked structure was formed.
- the screen printing silver paste was formed on a surface of two types of receiving substrates obtained using the supports (i) and (ii), respectively, using a screen plate of a metal mesh 250, 3 cm in length, A 1 cm wide rectangular area (area) was printed at a film thickness of 1 ⁇ m, and then dried at 150 ° C. for 30 minutes to obtain a printed matter (conductive pattern).
- the volume resistivity of the solid printed portion formed in the rectangular range of 3 cm in length and 1 cm in width formed on the surface of the printed matter (conductive pattern) obtained by the above-described method was measured using a Loresta pointer meter (MCP-T610 manufactured by Mitsubishi Chemical Corporation). It measured using.
- What volume resistivity is less than 5 ⁇ 10 -6 ⁇ ⁇ cm "A”, 5 ⁇ 10 -6 or 9 ⁇ 10 -6 ⁇ ⁇ less than cm "B what is sufficient available levels “C”, a level that is 9 ⁇ 10 ⁇ 6 or more and less than 5 ⁇ 10 ⁇ 5 ⁇ ⁇ cm and that can be used, and “C” that is 5 ⁇ 10 ⁇ 5 or more and less than 9 ⁇ 10 ⁇ 5 ⁇ ⁇ cm Was evaluated as “E” when it was “D”, 9 ⁇ 10 ⁇ 5 or more and difficult to use practically.
- An ink jet printer (Konica Minolta IJ Co., Ltd. Inkjet Testing Machine EB100, Evaluation Printer Head KM512L, Discharge Amount 42 pl) is applied to the surface of the receiving substrate obtained by using the support (ii).
- a printed product was obtained by printing a solid 5 cm long and 5 cm wide square area (area) with a film thickness of 0.5 ⁇ m and then drying at 150 ° C. for 30 minutes.
- the receiving substrates described in Examples 4 to 6 and Examples 8 to 11 were subjected to a drying process for 30 minutes at 150 ° C. after printing using the plating nucleating agent 1, whereby a receiving layer was obtained.
- a crosslinked structure was formed.
- An activator (A screen A220 manufactured by Okuno Pharmaceutical Co., Ltd.) is applied to the surface of the printed matter obtained above (the surface on which the plating nucleus is supported), and the plating nucleus is activated under the condition of 55 ° C. ⁇ 5 minutes. Processed.
- 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 X (plating structure X) in which a plating film made of copper was formed on the surface on which the plating nucleus was carried was obtained.
- a cellophane adhesive tape (manufactured by Nichiban Co., Ltd., CT405AP-24, 24 mm) is pressure-bonded to the plating film surface of the conductive pattern X (plating structure X) obtained above with a finger, and the cellophane adhesive tape is then electrically conductive. Peeling was performed in the direction of 90 degrees with respect to the surface of the pattern X (plating structure X). The adhesive surface of the peeled cellophane adhesive tape was visually observed, and the adhesiveness was evaluated based on the presence or absence of the adhering matter.
- A indicates that no adherent was observed on the adhesive surface of the peeled cellophane adhesive tape, and it is any of metal plating, silver, and receiving layer within a range of less than about 5% of the adhesive tape application area. Is peeled off from the support and adhered to the adhesive tape within a range of about 5% to less than 50% of the adhesive area of the “B” adhesive tape. "C” peels off the support and adheres to the adhesive tape, and the metal plating, silver, or receiving layer peels off from the support within a range of about 50% or more of the adhesive tape application area. The thing adhering to the tape was evaluated as "D".
- An ink jet printer (Konica Minolta IJ Co., Ltd. Inkjet Testing Machine EB100, Evaluation Printer Head KM512L, Discharge Amount 42 pl) is applied to the surface of the receiving substrate obtained by using the support (ii).
- a printed product was obtained by printing a solid 5 cm long and 5 cm wide square area (area) with a film thickness of 0.5 ⁇ m and then drying at 150 ° C. for 30 minutes.
- the receiving substrates described in Examples 4 to 6 and Examples 8 to 11 were subjected to a drying process for 30 minutes at 150 ° C. after printing using the plating nucleating agent 1, whereby a receiving layer was obtained.
- a crosslinked structure was formed.
- An activator (A screen A220 manufactured by Okuno Pharmaceutical Co., Ltd.) is applied to the surface of the printed matter obtained above (the surface on which the plating nucleus is supported), and the plating nucleus is activated under the condition of 55 ° C. ⁇ 5 minutes. Processed.
- a conductive pattern Y (plating structure Y) was obtained in which a plating film made of copper was laminated on the surface of the plating film made of copper of the conductive pattern X (plating structure X).
- a cellophane adhesive tape (manufactured by Nichiban Co., Ltd., CT405AP-24, 24 mm) is pressure-bonded to the plating film surface of the conductive pattern Y (plating structure Y) obtained above with a finger, and the cellophane adhesive tape is then electrically conductive. Peeling was performed in the direction of 90 degrees with respect to the surface of the pattern X (plating structure X). The adhesive surface of the peeled cellophane adhesive tape was visually observed, and the adhesiveness was evaluated based on the presence or absence of the adhering matter.
- A indicates that no adherent was observed on the adhesive surface of the peeled cellophane adhesive tape, and it is any of metal plating, silver, and receiving layer within a range of less than about 5% of the adhesive tape application area. Is peeled off from the support and adhered to the adhesive tape within a range of about 5% to less than 50% of the adhesive area of the “B” adhesive tape. "C” peels off the support and adheres to the adhesive tape, and the metal plating, silver, or receiving layer peels off from the support within a range of about 50% or more of the adhesive tape application area. The thing adhering to the tape was evaluated as "D”. The case where the plating film was not peeled or the plating was not deposited during the plating treatment step was designated as “E”.
- the receiving substrate obtained in Example 1 had excellent adhesion to the polyethylene terephthalate substrate and had good adhesion to both the polyimide substrate and the glass substrate.
- the printed matter obtained by printing the solvent-based pigment ink on the receiving substrate had excellent printability.
- the electroconductive pattern provided with the outstanding thin wire property and favorable electroconductivity was able to be obtained by printing various nano silver ink on the said receiving base material.
- the receiving substrate obtained in Example 2 had excellent adhesion to any of a polyethylene terephthalate substrate, a polyimide substrate, and a glass substrate.
- the printed matter obtained by printing the solvent-based pigment ink on the receiving substrate had excellent printability.
- the receiving substrate obtained in Example 3 had excellent adhesion to the polyethylene terephthalate substrate, and had good adhesion to both the polyimide substrate and the glass substrate. . Further, the printed matter obtained by printing the solvent-based pigment ink on the receiving substrate had good printability. In addition, by printing various types of nano silver ink on the receiving substrate, it is possible to obtain a conductive pattern having good thinness and electrical conductivity and durability enough to withstand plating treatment. It was.
- the receiving base material obtained in Examples 4 and 5 has a component that forms a crosslinked structure, it has excellent adhesion to any of a polyethylene terephthalate base material, a polyimide base material, and a glass base material. there were.
- the printed matter obtained by printing the solvent-based pigment ink on the receiving substrate had excellent printability.
- by printing various nano silver inks on the receiving substrate it was possible to obtain a conductive pattern that had excellent thin-line property and electrical conductivity and had durability that could withstand plating treatment.
- the receiving base material obtained in Example 6 had excellent adhesion to any of a polyethylene terephthalate base material, a polyimide base material, and a glass base material since a crosslinking agent was used in combination.
- the printed matter obtained by printing the solvent-based pigment ink on the receiving substrate had excellent printability.
- by printing various types of nano silver ink on the receiving substrate it is possible to obtain a conductive pattern having good thinness and electrical conductivity and durability enough to withstand plating treatment. It was.
- the receiving base material obtained in Example 7 had excellent adhesion to any of a polyethylene terephthalate base material, a polyimide base material, and a glass base material since a crosslinking agent was used in combination. Further, the printed matter obtained by printing the solvent-based pigment ink on the receiving substrate had good printability.
- the receiving base materials obtained in Examples 8 and 9 had excellent adhesion to any of a polyethylene terephthalate base material, a polyimide base material, and a glass base material. Further, the printed matter obtained by printing the solvent-based pigment ink on the receiving substrate had good printability. In addition, by printing various types of nano silver ink on the receiving substrate, it is possible to obtain a conductive pattern having good thinness and electrical conductivity and durability enough to withstand plating treatment. It was.
- the receiving substrate obtained in Example 10 had good adhesion to a polyethylene terephthalate substrate, a polyimide substrate and a glass substrate.
- the printed matter obtained by printing the solvent-based pigment ink on the receiving substrate had excellent printability.
- by printing various nano silver inks on the receiving substrate it was possible to obtain a conductive pattern that had excellent thin-line property and electrical conductivity and had durability that could withstand plating treatment.
- the receiving substrate obtained in Example 11 had excellent adhesion to the polyethylene terephthalate substrate and had good adhesion to both the polyimide substrate and the glass substrate. Further, the printed matter obtained by printing the solvent-based pigment ink on the receiving substrate had good printability. In addition, by printing various types of nano silver ink on the receiving substrate, it is possible to obtain a conductive pattern having good thinness and electrical conductivity and durability enough to withstand plating treatment. It was.
- the receiving substrate obtained in Comparative Example 1 using a urethane resin having an aliphatic cyclic structure ratio of 2000 mmol / kg or less is a polyethylene terephthalate substrate, a polyimide substrate, and a glass substrate. It did not have practically sufficient adhesion. Further, the printed matter obtained by printing the solvent-based pigment ink on the receiving base material does not have sufficient printability such as causing bleeding. In addition, even when various nano silver inks are printed on the receiving substrate, it may cause blurring of the image line, so that it was not possible to obtain a conductive pattern having good fineness and electrical conductivity. .
- the receiving substrate obtained in Comparative Example 2 using a urethane resin having an aliphatic cyclic structure ratio exceeding 5500 mmol / kg is practically sufficient for any of a polyethylene terephthalate substrate, a polyimide substrate and a glass substrate. It did not have good adhesion. Further, the printed matter obtained by printing the solvent-based pigment ink on the receiving base material does not have sufficient printability such as causing bleeding. In addition, even when various nano silver inks are printed on the receiving substrate, it may cause blurring of the image line, so that it was not possible to obtain a conductive pattern having good fineness and electrical conductivity. .
- the receiving base material obtained in Comparative Example 3 containing no vinyl polymer did not have practically sufficient adhesion to any of a polyethylene terephthalate base material, a polyimide base material, and a glass base material. Further, the printed matter obtained by printing the solvent-based pigment ink on the receiving base material does not have sufficient printability such as causing bleeding. In addition, even when various nano silver inks are printed on the receiving substrate, it may cause blurring of the image line, so that it was not possible to obtain a conductive pattern having good fineness and electrical conductivity. .
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Abstract
Description
また、前記焼成工程を経る際に、インク受容層である前記ラテックス層の過剰な膨潤及び変形等を引き起こしやすいため、電気回路等の断線や通電不良を引き起こす場合があった。また、前記ラテックス層は、前記焼成工程による加熱を行う前に、前記支持体に対して十分な密着性を有さない場合が多いため、前記焼成工程を経る前に、支持体とインク受容層との部分的な剥離を引き起こす場合があった。
前記受容層形成用樹脂組成物は、もっぱら、導電性物質や顔料等を含む流動体が接触した場合に、前記流動体中の溶媒を吸収し、前記導電性物質や顔料を担持する受容層の形成に使用できるものである。
前記3級アミノ基の一部又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類や、スルホン酸、メタンスルホン酸等の有機スルホン酸類、及び、塩酸、硫酸、オルトリン酸、オルト亜リン酸等の無機酸等を単独または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、塩素や硫黄等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。
前記その他のポリオール(a2-3)としては、例えば、前記したもの以外のポリエステルポリオール、ポリエーテルポリオール及びポリカーボネートポリオール等を使用することができる。
→膜厚の下限を変更しました。
前記導電性インクとしては、例えば導電性物質と溶媒と、必要に応じて分散剤等の添加剤を含有するものを使用することができる。
前記導電性物質を接合する方法としては、加熱焼成する方法や、光照射する方法が挙げられる。
温度計、窒素ガス導入管、攪拌器を備えた窒素置換された容器中で、ポリエステルポリオール(1,4-シクロヘキサンジメタノールとネオペンチルグリコールとアジピン酸とを反応させて得られたポリエステルポリオール、前記ポリエステルポリオール中の脂肪族環式構造含有量は1426mmol/kg、水酸基当量1000g/当量)を100質量部、2,2―ジメチロールプロピオン酸17.6質量部、1,4-シクロヘキサンジメタノール21.7質量部、ジシクロヘキシルメタンジイソシアネート106.2質量部を、メチルエチルケトン178質量部の混合溶剤中で反応させることによって、分子末端にイソシアネート基を有するウレタンプレポリマーの有機溶剤溶液を得た。
温度計、窒素ガス導入管、攪拌器を備えた窒素置換された容器中で、ポリエステルポリオール100質量部(ネオペンチルグリコールと1,6-ヘキサンジオールとアジピン酸とを反応させて得られたポリエステルポリオール、水酸基当量1000g/当量)、
2,2―ジメチロールプロピオン酸12.6質量部、1,4-シクロヘキサンジメタノール5.5質量部、ジシクロヘキシルメタンジイソシアネート58.2質量部を、メチルエチルケトン124質量部の混合溶剤中で反応させることによって、分子末端にイソシアネート基を有するウレタンプレポリマーの有機溶剤溶液を得た。
温度計、窒素ガス導入管、攪拌器を備えた窒素置換された容器中で、ポリエステルポリオール100質量部(1,4-シクロヘキサンジメタノールとネオペンチルグリコールとアジピン酸とを反応させて得られたポリエステルポリオール、前記ポリエステルポリオール中の脂肪族環式構造含有量:1426mmol/kg,水酸基当量1000g/当量)、2,2―ジメチロールプロピオン酸17.6質量部、1,4-シクロヘキサンジメタノール21.7質量部、ジシクロヘキシルメタンジイソシアネート106.2質量部を、メチルエチルケトン178質量部との混合溶剤中で反応させることによって、分子末端にイソシアネート基を有するウレタンプレポリマーの有機溶剤溶液を得た。
温度計、窒素ガス導入管、攪拌器を備えた窒素置換された容器中で、ポリエーテルポリオール100質量部(「PTMG2000」三菱化学株式会社製、水酸基当量1000g/当量)、2,2―ジメチロールプロピオン酸17.4質量部、1,4-シクロヘキサンジメタノール34.2質量部、ジシクロヘキシルメタンジイソシアネート109.3質量部を、イソホロンジイソシアネート31.5質量部を、メチルエチルケトン178質量部の混合溶剤中で反応させることによって、分子末端にイソシアネート基を有するウレタンプレポリマーの有機溶剤溶液を得た。
温度計、窒素ガス導入管、攪拌器を備えた窒素置換された容器中で、ポリカーボネートポリオール(1,4-シクロヘキサンジメタノールと炭酸エステルとを反応させて得られる脂肪族環式構造を含有するポリカーボネートジオール、前記ポリカーボネートポリオール中の脂肪族環式構造含有量は3000mmol/kg、水酸基当量1000g/当量)を100質量部、2,2―ジメチロールプロピオン酸9.7質量部、1,4-シクロヘキサンジメタノール5.5質量部、ジシクロヘキシルメタンジイソシアネート51.4質量部を、メチルエチルケトン111質量部の混合溶剤中で反応させることによって、分子末端にイソシアネート基を有するウレタンプレポリマーの有機溶剤溶液を得た。
温度計、窒素ガス導入管、攪拌器を備えた窒素置換された容器中で、ポリエーテルポリオール100質量部(「PTMG2000」三菱化学株式会社製、水酸基当量1000g/当量)、2,2―ジメチロールプロピオン酸7.9質量部、ネオペンチルグリコール3.0質量部、イソホロンジイソシアネート41.0質量部を、メチルエチルケトン118質量部の混合溶剤中で反応させることによって、分子末端にイソシアネート基を有するウレタンプレポリマーの有機溶剤溶液を得た。
次いで、前記ウレタン樹脂の有機溶剤溶液にトリエチルアミンを5.9質量部加えることで前記ウレタン樹脂が有するカルボキシル基の一部または全部を中和し、さらに水230質量部を加え十分に攪拌することによりウレタン樹脂の水性分散液を得た。
温度計、窒素ガス導入管、攪拌器を備えた窒素置換された容器中で、ポリエステルポリオール(1,4-シクロヘキサンジメタノールとネオペンチルグリコールとアジピン酸とを反応させて得られたポリエステルポリオール、前記ポリエステルポリオール中の脂肪族環式構造含有量は1425mmol/kg、水酸基当量は1000g/当量)を100質量部、2,2―ジメチロールプロピオン酸49.7質量部、1,4-シクロヘキサンジメタノール127.1質量部、ジシクロヘキシルメタンジイソシアネート416.8質量部を、メチルエチルケトン492質量部の混合溶剤中で反応させることによって、分子末端にイソシアネート基を有するウレタンプレポリマーの有機溶剤溶液を得た。
撹拌機、還流冷却管、窒素導入管、温度計、滴下漏斗を備えた反応容器に脱イオン水115質量部、ラテムルE-118B(花王株式会社製:有効成分25質量%)4質量部を入れ、窒素を吹き込みながら75℃まで昇温した。
前記で得たウレタン樹脂(A)-1の水分散体とビニル重合体(B)の-1の水分散体を、ウレタン樹脂(A)-1の水分散体:ビニル重合体(B-1)の水分散体=100:350(固形分質量比30:70)で混合し、不揮発分が20質量%になるように脱イオン水を使用した後、200メッシュ濾布で濾過することによって、本発明で使用する受容層形成用樹脂組成物(I-1)を得た。
(i)PET;ポリエチレンテレフタレートフィルム(東洋紡績株式会社製 コスモシャインA4300,厚さ50μm)
(ii)PI;ポリイミドフィルム(東レ・デュポン株式会社製Kapton200H,厚さ50μm)
(iii)GL;ガラス:ガラス板,JIS R3202,厚さ2mm
攪拌機、還流冷却管、窒素導入管、温度計、単量体混合物滴下用滴下漏斗、重合触媒滴下用滴下漏斗を備えた反応容器に脱イオン水140質量部、前記で得たウレタン樹脂(A)-1の水分散体100質量部を入れ、窒素を吹き込みながら80℃まで昇温した。
ウレタン樹脂の種類を下記表1に記載の(A)-1~(A)-3にそれぞれ変更し、、ビニル重合体の製造に使用するビニル単量体の組成を下記表1に記載の組成にそれぞれ変更すること以外は、実施例2記載の方法と同様の方法で、不揮発分20質量%の受容層形成用樹脂組成物(I-3)~(I-5)を調製した。
ウレタン樹脂の種類を下記表1に記載の(A)-1~(A)-5にそれぞれ変更し、ビニル重合体の製造に使用するビニル単量体の組成を下記表1及び2に記載の組成にそれぞれ変更すること以外は、実施例2記載の方法と同様の方法で、不揮発分20質量%の受容層形成用樹脂組成物(I-7)~(I-11)を調製した。
ウレタン樹脂の種類を下記表1に記載の(A)’-1~(A)’-2にそれぞれ変更し、ビニル重合体の製造に使用するビニル単量体の組成を下記表2に記載の組成にそれぞれ変更すること以外は、実施例2記載の方法と同様の方法で、不揮発分20質量%の受容層形成用樹脂組成物(I’-1)~(I’-2)を調製した。
前記で得たウレタン樹脂(A)-1の水分散体を受容層形成用樹脂組成物(I’-3)とした。
MMA:メタクリル酸メチル
BA :アクリル酸n-ブチル
NBMAM:N-n-ブトキシメチルアクリルアミド
HEMA;メタクリル酸2-ヒドロキシエチル
4HBA;4-ヒドロキシブチルアクリレート
MAA:メタクリル酸
架橋剤1;メラミン系化合物(DIC株式会社製 ベッカミンM-3、トリメトキシメチルメラミン)
前記ウレタン樹脂の製造に使用したポリオールやポリイソシアネート等の全原料の合計質量と、前記ウレタン樹脂の製造に使用した脂肪族環式構造を有する化合物(脂肪族環式構造を有するポリオールや脂肪族環式構造を有するポリイソシアネート)が有する脂肪族環式構造の物質量に基づいて算出した。
前記印刷を施す前の各受容基材の表面(受容層上)にセロハン粘着テープ(ニチバン株式会社製,CT405AP-24,24mm)を指で圧着した後、前記セロハン粘着テープを、受容基材の表面に対して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。
支持体として前記『(i)PET;ポリエチレンテレフタレートフィルム(東洋紡績株式会社製 コスモシャインA4300,厚さ50μm)』を用いて得られた受容基材表面に、インクジェットプリンター(Roland社製のSP-300V)を用い、流動体として、グリコール系高極性溶剤と顔料とを含む下記9色の溶剤系顔料インクを、下記に例示した順に重ねて印刷することによって、100%~400%ベタ画像の印刷物を得た。
・C100%インク
・Y100%インク
・M100%インク
・Bk100%インク
・C100%とM100%とからなる合計200%のインク
・M100%とY100%とからなる合計200%のインク
・Y100%とC100%とからなる合計200%のインク
・C100%とM100%とY100%とからなる合計300%のインク
・C100%とM100%とY100%とK100%とからなる合計400%のインク
[インクジェット印刷用ナノ銀インク1の調製]
ジエチレングリコールジエチルエーテル65質量部と、γ-ブチロラクトン18質量部と、テトラエチレングリコールジメチルエーテル15質量部と、テトラエチレングリコールモノブチルエーテル2質量部とからなる混合溶媒に、平均粒径30nmの銀粒子を分散させることによって、溶剤系インクジェット印刷用ナノ銀インク1を調製した。
テトラドデカンからなる溶媒に平均粒径30nmの銀粒子を分散させることによって、溶剤系インクジェット印刷用ナノ銀インク2を調製した。
銀 ペースト(ハリマ化成株式会社製 NPS)を用いた。
前記インクジェット印刷用ナノ銀インク1~2を、それぞれ、前記支持体(i)、(ii)及び(iii)を用いて得られた3種の受容基材表面に、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、膜厚0.5μmの直線を約1cm印刷し、次いで150℃の条件下で30分間乾燥することによって、それぞれ印刷物(導電性パターン)を得た。実施例4~6、8~11に記載の受容基材を用いた場合には、上記導電性インクを用いて印刷した後の、前記150℃の条件で30分間乾燥工程を経ることによって、受容層に架橋構造が形成された。架橋構造が形成されたか否かは、表3及び表4中に示すように、「常温(23℃)で乾燥し、その後70℃で加熱して形成された導電性インク受容層のゲル分率」と、「更に150℃で加熱することによって形成された導電性インク受容層のゲル分率」とに基づいて判断した。すなわち、150℃で加熱して得た導電性インク受容層のゲル分率が、常温乾燥した後、70℃で加熱して得た導電性インク受容層のゲル分率(未架橋状態)と比較して、25質量%以上増加したものを、高温加熱により架橋構造が形成されたと判断した。
前記スクリーン印刷用銀ペーストを、それぞれ、前記支持体(i)、(ii)及び(iii)を用いて得られた3種の受容基材表面に、メタルメッシュ250のスクリーン版を用いて、線幅50μm、膜厚1μmの直線を約1cm印刷し、次いで150℃の条件下で30分間乾燥することによって印刷物(導電性パターン)を得た。
実施例4~6、8~11に記載の受容基材については、上記インクを用いて印刷した後の、前記150℃の条件で30分間乾燥工程を経ることによって、インク受容層に架橋構造が形成された。架橋構造の有無は、前記と同様の方法で判断した。
前記した方法で得られた印刷物(導電性パターン)表面に形成された印刷部(線部)全体を、光学顕微鏡(株式会社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、該印刷部のにじみの有無を確認した。
前記インクジェット印刷用ナノ銀インク1を、それぞれ、前記支持体(i)及び(ii)を用いて得られた2種の受容基材表面に、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、縦3cm、横1cmの長方形の範囲(面積)を、膜厚0.5μmで印刷し、次いで150℃の条件下で30分間乾燥することによって、それぞれ印刷物(導電性パターン)を得た。実施例4~6、8~11に記載の受容基材を用いた場合には、上記インクを用いて印刷した後の、前記150℃の条件で30分間乾燥工程を経ることによって、インク受容層に架橋構造が形成された。
ジエチレングリコールジエチルエーテル65質量部と、γ-ブチロラクトン18質量部と、テトラエチレングリコールジメチルエーテル15質量部と、テトラエチレングリコールモノブチルエーテル2質量部とからなる混合溶媒に、平均粒径30nmの銀粒子(めっき核)を分散させることによって、溶剤系のめっき核剤1を調製した。
ジエチレングリコールジエチルエーテル65質量部と、γ-ブチロラクトン18質量部と、テトラエチレングリコールジメチルエーテル15質量部と、テトラエチレングリコールモノブチルエーテル2質量部とからなる混合溶媒に、平均粒径30nmの銀粒子(めっき核)を分散させることによって、溶剤系のめっき核剤1を調製した。
実施例2で得た受容基材は、ポリエチレンテレフタレート基材、ポリイミド基材及びガラス基材のいずれに対しても優れた密着性を有するものであった。また、前記受容基材に溶剤系顔料インクを印刷して得た印刷物は、優れた印刷性を備えたものであった。また、前記受容基材に各種ナノ銀インクを印刷することによって、細線性や通電性に優れ、かつ、めっき処理に耐えうるレベルの耐久性を備えた導電性パターンを得ることができた。
また、実施例3で得た受容基材は、ポリエチレンテレフタレート基材に対し優れた密着性を有し、ポリイミド基材及びガラス基材のいずれに対しても良好な密着性を有するものであった。また、前記受容基材に溶剤系顔料インクを印刷して得た印刷物は、良好な印刷性を備えたものであった。また、前記受容基材に各種ナノ銀インクを印刷することによって、良好な細線性と通電性とを備え、かつ、めっき処理に耐えうるレベルの耐久性を備えた導電性パターンを得ることができた。
実施例4及び5で得た受容基材は、架橋構造を形成する成分を有することから、ポリエチレンテレフタレート基材、ポリイミド基材及びガラス基材のいずれに対しても優れた密着性を有するものであった。また、前記受容基材に溶剤系顔料インクを印刷して得た印刷物は、優れた印刷性を備えたものであった。また、前記受容基材に各種ナノ銀インクを印刷することによって、細線性や通電性に優れ、かつ、めっき処理に耐えうるレベルの耐久性を備えた導電性パターンを得ることができた。
実施例6で得た受容基材は、架橋剤を併用していることから、ポリエチレンテレフタレート基材、ポリイミド基材及びガラス基材のいずれに対しても優れた密着性を有するものであった。また、前記受容基材に溶剤系顔料インクを印刷して得た印刷物は、優れた印刷性を備えたものであった。また、前記受容基材に各種ナノ銀インクを印刷することによって、良好な細線性と通電性とを備え、かつ、めっき処理に耐えうるレベルの耐久性を備えた導電性パターンを得ることができた。
実施例7で得た受容基材は、架橋剤を併用していることから、ポリエチレンテレフタレート基材、ポリイミド基材及びガラス基材のいずれに対しても優れた密着性を有するものであった。また、前記受容基材に溶剤系顔料インクを印刷して得た印刷物は、良好な印刷性を備えたものであった。また、前記受容基材に各種ナノ銀インクを印刷することによって、良好な細線性と通電性とを備え、かつ、めっき処理に耐えうるレベルの耐久性を備えた導電性パターンを得ることができた。
実施例8及び9で得た受容基材は、ポリエチレンテレフタレート基材、ポリイミド基材及びガラス基材のいずれに対しても優れた密着性を有するものであった。また、前記受容基材に溶剤系顔料インクを印刷して得た印刷物は、良好な印刷性を備えたものであった。また、前記受容基材に各種ナノ銀インクを印刷することによって、良好な細線性と通電性とを備え、かつ、めっき処理に耐えうるレベルの耐久性を備えた導電性パターンを得ることができた。
実施例10で得た受容基材は、ポリエチレンテレフタレート基材、ポリイミド基材及びガラス基材に対して良好な密着性を有するものであった。また、前記受容基材に溶剤系顔料インクを印刷して得た印刷物は、優れた印刷性を備えたものであった。また、前記受容基材に各種ナノ銀インクを印刷することによって、細線性や通電性に優れ、かつ、めっき処理に耐えうるレベルの耐久性を備えた導電性パターンを得ることができた。
Claims (19)
- ウレタン樹脂(A)、ビニル重合体(B)、及び、水性媒体(C)を含有する受容層形成用樹脂組成物であって、前記ウレタン樹脂(A)が、前記ウレタン樹脂(A)の全量に対して2,000mmol/kg~5,500mmol/kgの脂肪族環式構造と、親水性基とを有するものであることを特徴とする受容層形成用樹脂組成物。
- 前記ウレタン樹脂(A)と前記ビニル重合体(B)とが、前記ウレタン樹脂(A)であるシェル層と、前記ビニル重合体(B)であるコア層とによって構成される複合樹脂粒子(D)を形成する請求項1に記載の受容層形成用樹脂組成物。
- 前記受容層形成用樹脂組成物が、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樹脂組成物。
- 前記導電性物質または顔料を含む流動体が、導電性物質を含有する導電性インク、導電性物質を含有するめっき核剤、または、顔料を含有する顔料インクである請求項3に記載の受容層形成用樹脂組成物。
- 前記ビニル重合体(B)が、メタクリル酸メチルを10質量%~70質量%、及び、炭素原子数2~12のアルキル基を有する(メタ)アクリル酸アルキルエステルを10質量%~50質量%を含有するビニル単量体混合物を重合して得られるものである請求項1に記載の受容層形成用樹脂組成物。
- 前記複合樹脂粒子(D)を構成する前記ウレタン樹脂(A)と前記ビニル重合体(B)との質量割合[(A)/(B)]が、70/30~10/90の範囲である請求項2に記載の受容層形成用樹脂組成物。
- 前記ビニル樹脂(B)が、架橋性官能基を有するものである請求項1に記載の受容層形成用樹脂組成物。
- 前記架橋性官能基が、メチロールアミド基及びアルコキシメチルアミド基からなる群より選ばれる1種以上の熱架橋性官能基である請求項7に記載の受容層形成用樹脂組成物。
- 更に、架橋剤(E)を含有するものであって、前記架橋剤(E)が、100℃以上に加熱することによって架橋反応しうるものである請求項1または7に記載の受容層形成用樹脂組成物。
- 前記架橋剤(E)が、メラミン化合物、エポキシ化合物、オキサゾリン化合物、カルボジイミド化合物、及び、イソシアネート化合物からなる群より選ばれる1種以上の熱架橋剤(e1-2)である請求項9に記載の受容層形成用樹脂組成物。
- 支持体表面の一部または全部に、2,000mmol/kg~5,500mmol/kgの脂肪族環式構造と、親水性基とを有するウレタン樹脂(A)、ビニル重合体(B)、及び、水性媒体(C)を含有する受容層形成用樹脂組成物を用いて形成された受容層を有し、前記受容層が、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であることを特徴とする受容基材。
- 請求項11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。
- 前記印刷が、インクジェット印刷法、スクリーン印刷法、凸版反転印刷法またはグラビアオフセット印刷法によってなされたものである請求項12に記載の印刷物。
- 請求項11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。
- 請求項11に記載の受容基材に、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し、次いで前記印刷された前記受容層に架橋構造を形成することによって得られる導電性パターン。
- 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14または15に記載の導電性パターン。
- 請求項14~16のいずれか1項に記載の導電性パターンからなる導電回路。
- 支持体の表面の一部または全部に、2,000mmol/kg~5,500mmol/kgの脂肪族環式構造と、親水性基とを有するウレタン樹脂(A)、ビニル重合体(B)、及び、水性媒体(C)を含有する受容層形成用樹脂組成物を塗布し、前記受容層形成用樹脂組成物が架橋反応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、前記印刷された受容層を加熱することによって架橋構造を形成す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、2,000mmol/kg~5,500mmol/kgの脂肪族環式構造と、親水性基とを有するウレタン樹脂(A)、ビニル重合体(B)、及び、水性媒体(C)を含有する受容層形成用樹脂組成物を塗布し、前記受容層形成用樹脂組成物が架橋反応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、次いで、前記受容層の表面に、前記流動体を印刷することで、前記流動体中に含まれる導電性物質からなる印刷部を形成し、次いで、前記印刷された受容層を加熱することによって架橋構造を形成し、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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JP2016005909A (ja) * | 2014-05-30 | 2016-01-14 | トッパン・フォームズ株式会社 | 積層体及び電子機器 |
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Also Published As
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TW201317302A (zh) | 2013-05-01 |
US8784956B2 (en) | 2014-07-22 |
CN103201117B (zh) | 2015-08-19 |
KR101562576B1 (ko) | 2015-10-22 |
EP2620290A4 (en) | 2015-01-28 |
TWI515257B (zh) | 2016-01-01 |
JPWO2013035582A1 (ja) | 2015-03-23 |
CN103201117A (zh) | 2013-07-10 |
EP2620290B1 (en) | 2016-05-25 |
US20130260114A1 (en) | 2013-10-03 |
JP5177607B1 (ja) | 2013-04-03 |
EP2620290A1 (en) | 2013-07-31 |
KR20140059752A (ko) | 2014-05-16 |
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