WO2012176793A1 - Procédé de formation de motif, système de formation de motif et procédé de fabrication d'une structure de motif - Google Patents

Procédé de formation de motif, système de formation de motif et procédé de fabrication d'une structure de motif Download PDF

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Publication number
WO2012176793A1
WO2012176793A1 PCT/JP2012/065708 JP2012065708W WO2012176793A1 WO 2012176793 A1 WO2012176793 A1 WO 2012176793A1 JP 2012065708 W JP2012065708 W JP 2012065708W WO 2012176793 A1 WO2012176793 A1 WO 2012176793A1
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Prior art keywords
functional liquid
plating
group
pattern
discharge
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PCT/JP2012/065708
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English (en)
Japanese (ja)
Inventor
学 勝村
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富士フイルム株式会社
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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
    • H05K3/12—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns
    • H05K3/1241—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns by ink-jet printing or drawing by dispensing
    • 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
    • H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
    • H05K3/386—Improvement of the adhesion between the insulating substrate and the metal by the use of an organic polymeric bonding layer, e.g. adhesive
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/07—Treatments involving liquids, e.g. plating, rinsing
    • H05K2203/0703—Plating
    • H05K2203/0709—Catalytic ink or adhesive for electroless plating
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material

Definitions

  • the present invention relates to a pattern forming method, a pattern forming system, and a pattern structure manufacturing method. Specifically, a functional liquid pattern forming method, a conductive pattern forming method, a functional liquid pattern forming system, a conductive pattern forming system, The present invention relates to a method for producing a functional liquid pattern structure and a method for producing a conductive pattern structure. The present invention particularly relates to a technique for forming a fine pattern using an ink jet method.
  • a photolithographic method is known as a method for manufacturing a wiring board.
  • a resist layer made of a dry film resist or a liquid resist is formed on a copper clad laminate made of an insulating layer and a copper foil, and the resist layer is irradiated with ultraviolet rays through a photomask, and pattern exposure (development). By doing so, the resist layer is patterned, and the copper foil portion not covered with the resist pattern is removed by etching to obtain a conductor pattern.
  • the photolithographic method needs to produce a photomask used for exposure of the resist layer.
  • a resist developing process as an intermediate material is required.
  • wiring drawing by printable electronics using a printing technique has been proposed.
  • the method of directly patterning conductive fine particle materials using an ink jet method is an alternative to the photolithographic method in that a wiring substrate can be manufactured on demand without a mask, and resist development and wiring etching processes can be reduced. Expected as a technology.
  • Patent Document 1 forms a conductive substance adsorbing resin precursor layer on the surface of a flexible resin film substrate, and forms a conductive substance adsorbing layer by applying energy to the conductive substance adsorbing resin precursor layer. Then, a conductive material is adsorbed on the conductive substance adsorption layer to form a conductive layer, and a metal layer adsorbed on the conductive adsorption resin layer is plated to form a conductive layer (metal layer). Yes.
  • a conductive material adsorption precursor layer is formed between a conductive (metal) layer made of a plating metal and a substrate surface, whereby the substrate surface and the conductive layer are referred to. Ensuring adhesion of dissimilar materials.
  • the coating liquid used as the conductive substance adsorption precursor layer contains a compound having a functional group capable of adsorbing metal ions or metal fine particles, and the coating liquid is applied by an ink jet method by adjusting the viscosity of the coating liquid. .
  • Patent Document 2 a liquid containing an unsaturated compound capable of radical polymerization is arranged on a substrate surface in a pattern by an ink jet method, radical polymerization is generated by heating or exposure, and a graft polymer is applied only to a liquid arrangement region.
  • a method for forming a conductive pattern (graft polymer pattern) is disclosed in which a conductive pattern is formed by attaching a conductive substance to the graft polymer.
  • Patent Document 2 discloses that heat treatment is performed in the graft polymer production step.
  • Patent Document 3 discloses a substrate in which a composition containing a photoradical generator is applied in a pattern on a substrate, the photoradical generator is immobilized on a substrate by heating or exposure, and the photoradical generator is immobilized.
  • a compound having a polymerizable double bond is brought into contact with the material, energy is applied to the surface of the base material, a graft polymer is formed in a region where the photo radical generator is present, and no material is present in the region where the graft polymer is formed.
  • a method for forming a conductive pattern in which a precursor of an electroplating catalyst or an electroless plating catalyst is applied, an electroless plating treatment is performed, and a conductive pattern is formed in a region where the graft polymer is formed. ing.
  • the adhesion between the substrate and the conductive pattern is enhanced by interposing a graft polymer between the substrate and the conductive pattern.
  • Patent Document 3 discloses an alcohol solvent, a ketone solvent, a nitrile solvent, and an ester solvent as solvents used in a composition containing a polymerizable compound, and when a cyano group-containing polymerizable polymer is used.
  • Amide type, ketone type and nitrile type solvents are preferred, and solvents having a boiling point of 50 ° C. to 150 ° C. are preferred.
  • the pattern formation by the functional liquid (liquid composition) using the ink jet method must consider the characteristics of the functional liquid and the environmental conditions.
  • the line width becomes non-uniform due to the occurrence of a bulge (a phenomenon in which the line width becomes wide), or jaggy (a part of the pattern is cut off). It is necessary to avoid abnormal pattern edge shapes and pattern breaks due to the occurrence of a phenomenon.
  • Patent Documents 1 to 3 described above disclose a technique for forming a layer (pattern) that serves as a base for plating and can ensure adhesion with a substrate using an ink jet method, stable ejection characteristics are disclosed. No specific ink jet system application conditions for obtaining a desired pattern or forming a preferable pattern are disclosed.
  • the present invention has been made in view of such circumstances, and a functional liquid pattern forming method, a conductive pattern forming method, and a functional liquid pattern forming system capable of forming a preferable fine pattern while avoiding the occurrence of bulges, jaggies and the like.
  • Another object is to provide a conductive pattern forming system, a functional liquid pattern structure manufacturing method, and a conductive pattern structure manufacturing method.
  • a functional liquid pattern forming method includes a catalyst-supporting polymer compound for plating, a high boiling point solvent having a boiling point of 190 ° C. or higher and lower than 245 ° C., and 75 ° C. or higher and lower than 105 ° C.
  • a heating step of heating the base material from the start of discharge to the end of discharge, and the predetermined discharge condition is a diameter D when the droplets of the functional liquid in flight are considered to be spherical.
  • the diameter D 1 when the droplet of the functional liquid in flight is regarded as a spherical shape, the substrate dot spacing W of the functional liquid that is formed in the upper, the diameter D 2 of the dots of the functional liquid that is formed on said substrate, by satisfying the relation of D 1 ⁇ W ⁇ D 2, bulges and jaggies Can be prevented.
  • the wetting and spreading of the functional liquid is suppressed by heating the base material while discharging the functional liquid.
  • the flowchart which shows the flow of the conductive pattern formation method which concerns on embodiment of this invention.
  • the flowchart which shows the detail of the catalyst support polymer discharge process for plating shown in FIG. Explanatory drawing which illustrated typically the pattern formation system applied to the catalyst carrying
  • the block diagram which shows schematic structure of the control system of the pattern formation system shown in FIG.
  • Explanatory drawing of discharge parameters of catalyst-supported polymer liquid for plating Graph showing the relationship between the boiling point of the solvent and the pattern width of the catalyst-supporting polymer solution for plating Graph showing the relationship between substrate temperature and pattern width Graph showing the relationship between dot pitch and pattern width
  • Explanatory drawing schematically showing the shape of the pattern for each dot pitch Explanatory drawing which shows the planar shape and three-dimensional shape of a pattern when forming a lamination pattern
  • Explanatory drawing showing the effect of volatility of mixed solvent on surface shape of dots (pattern)
  • Explanatory drawing which shows the relationship between the pitch between dots when forming a four-layer pattern and the planar shape of the pattern
  • FIG. 1 is a flowchart showing a flow of a conductive pattern forming method according to an embodiment of the present invention.
  • the conductive pattern forming method shown in this example is obtained by laminating a base material (for example, a 1 mm thick glass epoxy substrate with a 30 ⁇ m thick flattening film (epoxy insulating film)).
  • An adhesion auxiliary layer forming step for forming an adhesion auxiliary layer on the substrate step S10, and forming a pattern of the catalyst-supporting polymer for plating corresponding to the conductive pattern on the base material on which the adhesion auxiliary layer is formed by an ink jet method.
  • an adhesion auxiliary layer solution is applied on the substrate in order to ensure adhesion between the substrate and the catalyst-supporting polymer for plating.
  • an epoxy primer having a thickness of 3 micrometers is applied by spin coating.
  • an ink jet method may be applied to form a pattern corresponding to the conductive pattern.
  • NBR nonionic rubber
  • aqueous dispersant as an adhesion auxiliary layer liquid for forming an adhesion auxiliary layer
  • Latex-based materials may be applied.
  • the ink is diluted to a viscosity (about 10 millipascal second (centipoise)) that can be discharged by the ink jet method using a predetermined solvent.
  • a hydrophobic treatment that imparts a curing treatment by heating (for example, at a temperature of 100 ° C. or higher for 2 hours or less, preferably 1 hour or less), a treatment solution in which an acidic compound or a polyvalent metal salt is dissolved. And a cleaning process using a predetermined cleaning liquid is performed to form an adhesion auxiliary layer.
  • a plating catalyst-carrying polymer liquid (functional liquid) is applied to the adhesion auxiliary layer formed on the substrate by an ink jet method.
  • the catalyst-supporting polymer liquid for plating contains at least two kinds of solvents having different boiling points.
  • two or more kinds of solvents having different boiling points there may be an embodiment including a high boiling point solvent and a low boiling point solvent.
  • an embodiment including a medium-boiling solvent is also possible.
  • the “high boiling point solvent” is a solvent having a boiling point of 190 ° C. or higher and lower than 245 ° C., and examples thereof include diethylene glycol monoethylene ether (boiling point 196 ° C.) and propylene carbonate (boiling point 240 ° C.).
  • the “low boiling point solvent” is a solvent having a boiling point of 75 ° C. or higher and lower than 105 ° C., and examples thereof include water (boiling point 100 ° C.) and acetrinitol (boiling point 82 ° C.).
  • the “medium boiling point solvent” is a solvent having a boiling point of 105 ° C. or higher and lower than 190 ° C., and examples thereof include cyclohexane (boiling point 160 ° C.).
  • the effect of containing a low boiling point solvent in the plating catalyst-carrying polymer liquid is verified by an experiment using a plating catalyst-carrying polymer liquid containing water and acetrinitol (Details) Later).
  • the open time of the nozzle is increased by including a high boiling point solvent.
  • the “nozzle open time” is an index for drying the nozzle of the inkjet head, and is a time during which recovery is possible only by jetting (preliminary ejection) while leaving the nozzle uncovered.
  • the low boiling point solvent quickly evaporates after landing on the substrate, the volume of the droplet is reduced, and the droplet can be miniaturized.
  • the boiling point of the low boiling point solvent is less than the lower limit of the above range, when the plating catalyst-carrying polymer liquid is discharged, the plating catalyst-carrying polymer liquid is thickened in the vicinity of the nozzle, causing abnormal discharge or non-ejection. It can be a cause of occurrence.
  • the medium boiling point solvent has a high ability to dissolve the polymer substance as the content.
  • the above-described cyclohexane is a preferable substance as a medium-boiling point solvent because it has a high ability to dissolve a polymer substance having a property of being cross-linked and cured by reacting with light.
  • two or more types of solvents may be mixed as the high boiling point solvent, the medium boiling point solvent, and the low boiling point solvent.
  • a method for calculating the boiling point of the mixed solvent will be described later.
  • the catalyst-supporting polymer for plating is a polymer containing a functional group (interactive group) that forms an interaction with the electroless plating catalyst or its precursor and a polymerizable functional group.
  • a curing energy application process such as heat treatment (drying process) or exposure is performed (a curing energy application process: step S14).
  • heat treatment drying treatment
  • heating by a heater and spraying of dry air can be mentioned.
  • the conditions of 5 minutes to 120 minutes are mentioned at the temperature of 100 degreeC or more and 300 degrees C or less.
  • the exposure process light irradiation with a UV lamp, visible light, or the like can be given.
  • the light source include a mercury lamp, a metal halide lamp, a xenon lamp, a chemical lamp, and a carbon arc lamp.
  • an electron beam, an X-ray, an ion beam, a far infrared ray, or the like may be applied, or a g-line, i-line, deep-UV light, high-density energy beam (laser beam), or the like may be used.
  • the exposure time when scanning exposure using an infrared laser, high-illuminance flash exposure such as a xenon discharge lamp, or infrared lamp exposure varies depending on the reactivity of the polymer and the type of light source, but is generally 10 seconds to 5 hours. Between.
  • the exposure energy is appropriately selected depending on the material used, and the curing energy is preferably 30 milliwatts per square centimeter or more and 1500 milliwatts per square centimeter or less.
  • a plating catalyst or a plating catalyst precursor is applied to the cured plating catalyst-supporting polymer.
  • the plating catalyst include metal catalysts such as gold, silver and palladium.
  • a metal ion is mentioned as a catalyst precursor for plating.
  • the substrate on which the pattern of the catalyst-supporting polymer for plating is formed is immersed in a solution of a metal serving as a catalyst for plating such as gold, silver, and palladium.
  • a metal serving as a catalyst for plating such as gold, silver, and palladium.
  • the electroless plating process is performed on the pattern of the catalyst-carrying polymer to which the catalyst for plating or the catalyst precursor for plating has been applied.
  • a plating metal for example, copper
  • the plating film to be a conductive pattern has excellent conductivity with a high electric conductivity of 10 ⁇ 10 6 Siemens per meter or more and 100 ⁇ 10 6 Siemens per meter or less, and between the catalyst-supporting polymer for plating Excellent adhesion.
  • the type of plating performed in this step is preferably electroless plating from the viewpoint of improving the formability and adhesion of a hybrid structure that appears in the catalyst-supporting polymer for plating. Further, in order to obtain a plating layer having a desired film thickness, it is a more preferable aspect that electroplating is further performed after electroless plating.
  • the plating catalyst-carrying polymer provided with the plating catalyst or the plating catalyst precursor functions as a seed layer
  • the plating catalyst-carrying polymer can be electroplated.
  • the type of plating can be appropriately selected depending on the function of the plating catalyst or the plating catalyst precursor that forms an interaction with the plating catalyst-supporting polymer.
  • FIG. 2 is a flowchart showing the flow of the plating catalyst-carrying polymer discharging step (step S12 in FIG. 1). As shown in the figure, when the plating catalyst-carrying polymer discharge step is started (step S20), discharge conditions corresponding to the width of the conductive pattern are set in the discharge condition setting step (step S22), and the heating step (Step S24) starts heating the substrate on which the conductive pattern is formed.
  • the discharge conditions set by the discharge condition setting step include the diameter (dot size) D 1 of dots formed on the substrate, the pitch W between dots, and the diameter of the droplets during discharge (discharge droplet diameter) D 2. Is included.
  • the dot size D 1 , the dot pitch W, and the discharge droplet diameter D 2 are determined so as to satisfy the relationship of the following formula (11).
  • the discharge conditions for forming the first layer pattern and the discharge conditions for forming the second and subsequent patterns may be the same or different (details will be described later).
  • the heating step is to maintain the surface temperature of the base material within a certain range while the catalyst-supporting polymer liquid for plating is discharged.
  • the surface temperature of the substrate is maintained at 45 ° C. or higher, preferably 60 ° C. or higher.
  • step S26 On the basis of the discharge conditions set in the discharge condition setting step (step S22), when the discharge of the plating catalyst-supporting polymer liquid is started (step S26), the plating catalyst-supporting polymer liquid is set to a predetermined value.
  • a continuous pattern of the polymer liquid for supporting a catalyst for plating is formed by continuously discharging at a discharge cycle.
  • step S28 When the continuous pattern of the catalyst supporting polymer solution for plating is formed, the discharge is finished (step S28), the heating of the substrate is stopped (step S30), and the plating catalyst supporting polymer discharging step is finished (step). S32).
  • FIG. 3 is an explanatory view schematically showing a pattern forming system applied to the plating catalyst-carrying polymer discharging step shown in FIG.
  • a pattern forming system 10 shown in FIG. 1 discharges a catalyst-carrying polymer solution 16 for plating to the platen 14 that supports the back side surface of the substrate 12 and the surface of the substrate 12 (the surface on which the adhesion auxiliary layer 20 is formed).
  • the base material 12 has a flattened film 12B formed on an epoxy substrate 12A.
  • the base material 12 shown in FIG. 3 is coated with an epoxy primer agent (adhesion auxiliary layer) 20 by spin coating.
  • the platen 14 includes a heater 22 and is provided with a temperature sensor 24 that detects the temperature of the surface of the platen 14 (the support surface of the base material 12). The amount of heating by the heater 22 is determined based on the detection result of the temperature sensor 24. By controlling, the surface temperature of the base material 12 is maintained within a certain range.
  • the inkjet head 18 is configured to be movable with a predetermined clearance maintained between the inkjet head 18 and the surface of the substrate 12 by a moving mechanism (not shown). For example, an aspect in which the inkjet head 18 is moved two-dimensionally (in the xy direction) on a plane parallel to the surface of the substrate 12 is possible.
  • a full line type head having at least one nozzle row in which a plurality of nozzles are arranged over a length corresponding to the entire width of the base material 12 is provided, and the base material 12 and the inkjet head 18 are arranged in a direction perpendicular to the nozzle arrangement direction.
  • a mode of relatively moving the two is also possible.
  • a nozzle for discharging the catalyst-supporting polymer liquid for plating a liquid chamber (pressure chamber) communicating with the nozzle, and a pressurizing element for pressurizing the liquid in the liquid chamber are provided. There is an aspect to provide.
  • a piezoelectric element that deforms the liquid chamber or a heating element that heats the liquid in the liquid chamber can be applied.
  • a curing energy applying unit (not shown in FIG. 3) for applying curing energy to the pattern of the catalyst-supporting polymer solution for plating formed on the substrate 12 (shown by adding a reference numeral 26 to the dots of the catalyst-supporting polymer solution for plating).
  • a reference numeral 46 is shown in FIG.
  • the substrate on which the pattern of the catalyst-carrying polymer for plating is formed is moved to the curing energy application region of the curing energy application unit, and the curing energy is applied.
  • FIG. 4 is a block diagram showing a schematic configuration of a control system of the pattern forming system 10 shown in FIG.
  • the pattern forming system 10 includes a system control unit 30, an input / output interface (input / output I / F) 32, a liquid information acquisition unit 34, a memory 35, a heater control unit 36, and a discharge.
  • the control part 38, the conveyance control part 40, and the hardening energy provision control part 42 are comprised.
  • the system control unit 30 includes a central processing unit (CPU) and its peripheral circuits, and performs communication control with a host computer (not shown), read / write control of the memory 35, and control for controlling each unit. Generate signals and control them centrally.
  • CPU central processing unit
  • host computer not shown
  • read / write control of the memory 35 and control for controlling each unit. Generate signals and control them centrally.
  • the input / output interface 32 is an interface for inputting data (pattern data of the catalyst-supporting polymer liquid for plating) and outputting information to the outside, and a serial interface and a parallel interface are appropriately applied.
  • the liquid information acquisition unit 34 acquires information on the catalyst-supporting polymer liquid for plating and sends the information to the system control unit 30.
  • the liquid information acquisition unit 34 may read information stored in an information storage body such as a barcode or an IC tag, or may input the information by an operator.
  • the memory 35 functions as a temporary storage area for the pattern data of the catalyst-carrying polymer liquid for plating input via the input / output interface, an arithmetic processing area for data processing, and a storage area for system parameters.
  • various storage elements such as a semiconductor storage element and a magnetic storage element can be applied. Further, a mode in which a plurality of memory elements are used in combination is also possible.
  • the heater control unit 36 controls on / off and heating amount of the heater 22 built in the platen 14 shown in FIG. 3 based on a command signal sent from the system control unit 30 based on the detection result of the temperature sensor 24.
  • the discharge controller 38 converts the pattern data of the plating catalyst-carrying polymer liquid input via the input / output interface 32 into dot data based on preset discharge conditions, and the ink jet head 18 based on the dot data is converted. A drive voltage is generated.
  • the discharge control unit 38 includes a discharge condition setting unit that sets discharge conditions, an arithmetic processing unit that converts the input pattern data of the catalyst-carrying polymer liquid for plating into dot data, and a drive voltage (drive waveform based on the dot data). And a drive voltage generation unit.
  • the discharge conditions for forming the first layer (lowermost layer) pattern and the discharge conditions for forming the second and subsequent patterns may be the same. However, different conditions may be used.
  • the drive voltage generation unit includes a drive waveform generation unit, an amplification processing unit that performs voltage amplification and current amplification on the drive waveform, and an output unit that outputs the drive waveform after amplification processing as a drive voltage.
  • the conveyance control unit 40 controls the operation of the conveyance driving unit 44 that relatively moves the inkjet head 18 and the platen 14 (base material 12) based on the pattern data (dot data) of the catalyst-carrying polymer liquid for plating.
  • the conveyance driving unit 44 includes a moving mechanism that moves the inkjet head 18 along a guide, and a motor that is a driving source of the moving mechanism.
  • An aspect including a position detection element that detects the position of the inkjet head 18 and the position of the platen 14 (base material 12) is preferable.
  • Examples of the position detecting element include a rotary encoder attached to a rotating shaft of a motor and a linear encoder provided extending in the moving direction of the inkjet head 18.
  • the curing energy application control unit 42 controls the operation of the curing energy application unit 46 based on a command signal from the system control unit 30.
  • FIG. 5 is a view for explaining discharge parameters of the catalyst-supporting polymer liquid for plating.
  • parts that are the same as or similar to those in FIG. 3 are given the same reference numerals, and descriptions thereof are omitted.
  • the diameter of the discharge droplet 16 discharged from the inkjet head 18 (the diameter obtained from the volume of the discharge droplet 16 assuming that the shape of the discharge droplet 16 is a spherical shape) D 1 , the dot 26 formed on the substrate D 2 (the diameter of a dot in a state where the ejected droplets 16 land on the substrate independently and the shape is stable) D 2 , and the inter-dot pitch W of the dots 26 formed on the substrate is as shown in the figure. Yes.
  • the molecular weight of the polymer is preferably 50000 or less, and more preferably 20000 or less.
  • the mass ratio of the high molecular weight polymer is decreased, the discharge performance is improved, the nozzle is prevented from drying, and the open time is increased. If the mass ratio of the high molecular weight polymer is 10 mass percent or more, normal ejection may not be performed. Therefore, the mass ratio of the high molecular weight polymer is preferably less than 10 mass percent.
  • FIG. 6 is a graph showing the relationship between the boiling point (volatility) calculated from the mass ratio in a mixed solvent in which a plurality of types of solvents having different boiling points are mixed and the pattern width of the plating catalyst-carrying polymer liquid.
  • the temperature of a base material is room temperature (25 degreeC).
  • the boiling point of the mixed solvent in the figure is T 1 ° C.
  • the high boiling point solvent (19% by mass), the medium boiling point solvent (30.95% by mass) and the low boiling point solvent (45% by mass) in the above-described mass ratio are contained.
  • the catalyst-supporting polymer liquid for plating is used.
  • the boiling point of the mixed solvent is compared to the case where the boiling point is T 1 ° C. It can be seen that the pattern width has increased.
  • the pattern width is further increased as compared with the case where the boiling point of the solvent is T 2 ° C. It is understood.
  • the volatility (the boiling point of the mixed solvent calculated from the mass ratio) and the pattern width are correlated, and the pattern width is greatly reduced compared to the mixing of the low boiling point solvent (when the boiling point of the mixed solvent is lower). Is grasped.
  • FIG. 7 is a graph showing the relationship between the temperature of the substrate and the pattern width. As shown in the figure, it is understood that the pattern width decreases when the temperature of the substrate is gradually increased from room temperature (25 ° C.).
  • the pattern width can be reduced. Further, by making the surface temperature of the substrate 60 or more, the pattern width can be further miniaturized.
  • FIG. 8 is a graph showing the relationship between the inter-dot pitch and the pattern width.
  • FIGS. 9A to 9G show the inter-dot pitch and the planar shape of the pattern (micrographs are schematically shown). It is explanatory drawing which shows a relationship.
  • the substrate temperature is 60 ° C.
  • the inter-dot pitch W is quantitatively changed from a half of the diameter D 1 of the ejected droplets to the diameter D 2 of the dots.
  • D 1 in the above formula (11) 20 micrometers, and as an example of the dot ⁇ BR> f diameter (D 2 in the above formula (11)) formed on the base material, 60 ⁇ m. Can be micrometer.
  • the pattern width decreases by increasing the inter-dot pitch.
  • the dot pitch W and the diameter D 2 of the dots as shown in (f) of FIG. 9 approximately equal pitch between dots W as shown in (g) of FIG. 9>
  • jaggy a phenomenon in which a part of the pattern is cut
  • dot pitch W as shown in (e) of FIG. 9 is slightly smaller than the diameter D 2 of the dots, but there are portions where the thickness is reduced to the edge of the pattern, the jaggy patterns has occurred Absent.
  • the inter-dot pitch W When the inter-dot pitch W is reduced (when the dot density of the pattern is increased), the liquid amount per unit length of the pattern (liquid volume) increases, so that the pattern width increases. Therefore, in order to further reduce the pattern width, it is preferable to increase the inter-dot pitch W to reduce the liquid amount per unit length.
  • the inter-dot pitch W is set to the diameter D of the ejected droplet while suppressing the amount of droplet per unit length of the pattern. be a value greater than 1, it is possible to connect reliably dots which are adjacent to the pitch W of the dot diameter of less than D 2 between dots.
  • the diameter of the nozzle is 21 micrometers
  • the diameter of the ejected droplet is estimated to be about 25 micrometers, so the inter-dot pitch W is set to a value exceeding 25 micrometers.
  • the cause of the uneven pattern width is considered to be bulges.
  • the discharge frequency is 1 kilohertz or more, bulges are generated at non-uniform intervals.
  • the inter-dot pitch W and the discharge droplets are so arranged that the inter-dot pitch W exceeds the discharge droplet diameter (D 1 ) and is less than the dot diameter (D 2 ) so that adjacent dots overlap.
  • D 1 and D 2 satisfies the relationship of the above formula (11) and an appropriate dot pitch W is selected, as shown in (c) to (e) of FIG.
  • a fine pattern having a good planar shape can be formed.
  • the dot pitch W by the following one-half of the dot diameter D 2 (W ⁇ D 2/ 2), can form a more preferable fine laminate pattern.
  • the pattern forming method (system) of the catalyst-supporting polymer for plating configured as described above, good discharge performance by the in-jet method is ensured because the catalyst-supporting polymer liquid for plating contains a high boiling point solvent, and When the catalyst-supporting polymer liquid for plating contains a low boiling point solvent, wetting and spreading of the liquid is suppressed, and the pattern of the catalyst-supporting polymer for plating can be miniaturized.
  • FIG. 10 is explanatory drawing which illustrated typically the planar shape (upper figure) and three-dimensional shape (lower figure) of the pattern of the catalyst support polymer liquid for plating of a single layer (one layer).
  • the low boiling point solvent is 45% by mass
  • the medium boiling point solvent is 30.95% by mass
  • the high boiling point solvent is 19% by mass
  • the surface temperature is maintained at 60 ° C. by heating the substrate. ing.
  • planar shape shown in the upper part of FIGS. 10A to 10C schematically shows an image of a micrograph
  • the three-dimensional shape shown in the lower part schematically shows an image obtained by a shape measuring microscope. Is.
  • FIG. 10A shows a pattern of a single layer catalyst-supporting polymer liquid for plating. Although the pattern is miniaturized, the film thickness (d 1 ) is insufficient.
  • FIG. 10B shows a pattern of the catalyst-supporting polymer liquid for plating obtained by laminating two layers of the pattern of the catalyst-supporting polymer liquid for plating shown in FIG. As shown in the figure, the film thickness is about twice (d 1 ⁇ 2) while the fine width of the pattern is substantially maintained.
  • FIG. 10C shows a pattern of a catalyst-supporting polymer liquid for plating obtained by laminating four layers of the pattern shown in FIG.
  • the film thickness is not a value obtained by multiplying the film thickness of the single layer by the number of layers, but is approximately three times the film thickness of the single layer (d 1 ⁇ 3 ).
  • the pattern of the catalyst-supporting polymer liquid for plating can be laminated, and a multilayer (laminated) pattern having a desired film thickness can be formed by repeating the formation of a single layer pattern.
  • FIG. 11 are explanatory diagrams showing the influence of the volatility of the mixed solvent on the surface shape of the dot (pattern).
  • (A) of FIG. 11 shows a mixed solvent (boiling point T 1 ° C. shown in FIG. 6) in which 45% by mass of the low boiling point solvent, 30.95% by mass of the medium boiling point solvent, and 19% by mass of the high boiling point solvent are mixed. It represents the three-dimensional shape of the dot in which the catalyst-supporting polymer liquid for plating using a mixed solvent) is used.
  • the dots 26A shown in the figure have no extreme unevenness.
  • FIG. 11 shows a catalyst-supporting polymer solution for plating using a solvent in which a medium-boiling point solvent is added instead of a high-boiling point solvent and a low-boiling point solvent (only a medium-boiling point solvent having a boiling point of T 2 ° C. shown in FIG. 6). It represents the three-dimensional shape of the dots. In the dot 26B shown in the figure, extreme unevenness is generated at the end (portion surrounded by a circle), and so-called coffee stain phenomenon occurs.
  • (C) in FIG. 11 is for plating using a mixed solvent (a mixed solvent having a boiling point of T 3 ° C. shown in FIG. 6) in which a high boiling point solvent is mixed by 19% by mass and a medium boiling point solvent is mixed by 75.95% by mass. It represents a three-dimensional shape of dots in which a catalyst-supporting polymer liquid is used.
  • the dots 26C shown in the figure do not have extreme unevenness like the dots 26A shown in FIG.
  • the evaporation of the solvent at the dots on the substrate occurs from the boundary between the substrate, the dots and the gas. Convection occurs from the center of the dot to the end of the dot due to evaporation of the solvent, and the polymer component is carried by this convection, so that the localization of the polymer component occurs at the end of the dot, and the end of the dot is convex after drying. It becomes.
  • the rate of evaporation from the boundary between the substrate, dots, and gas (atmosphere) decreases, and convection flows from the center of the dot to the edge of the dot. And the dots are flattened after drying.
  • FIG. 12 is an explanatory diagram showing the relationship between the pitch between dots and the planar shape of the pattern when forming (stacking) the second and subsequent layers.
  • (A) of FIG. 12 is a case where substantially the same as the diameter D 1 of the ejected droplet dot pitch W, sometimes the second or upper layer protrudes from the width of the pattern.
  • (E) in FIG. 12 shows a case where the pitch between dots is substantially the same as the diameter of the dots, and jaggies are generated in the same manner as in (f) and (g) in FIG.
  • the pitch between dots W by the following one-half of the dot diameter D 2 (W ⁇ D 2/ 2), can form a more preferable fine laminate pattern.
  • the liquid is easy to spread because the properties of the liquid that forms the lower layer and the liquid that forms the upper layer are the same, making it difficult to form the laminated pattern.
  • the dot drying process is optimized by including a high boiling point solvent in the catalyst-supporting polymer solution for plating.
  • the surface shape of the film becomes good (more flattened).
  • the substrate by heating the substrate to a surface temperature of 60 ° C., wetting and spreading of the catalyst-supporting polymer liquid for plating can be prevented, and the pattern can be made finer. Furthermore, by including a low boiling point solvent in the catalyst-supporting polymer liquid for plating, it is possible to enhance the effect of preventing the wetting and spreading of the catalyst-supporting polymer liquid for plating.
  • the relationship between the diameter D 1 of the ejected droplets, the diameter D 2 of the dots, and the pitch W between dots satisfies the above formula (11), so that a preferable laminated pattern Is formed.
  • the number of stacked layers is preferably about 2 to 4.
  • the discharge conditions in the pattern formation for the second and subsequent layers are specified, but the discharge conditions can be applied to the discharge conditions for forming the first layer (lowermost layer) pattern. It is also possible to share the discharge conditions for forming the first layer pattern and the discharge conditions for forming the second and subsequent layers.
  • the substrate (substrate) applied to the present invention is preferably dimensionally stable.
  • the substrate (substrate) applied to the present invention is preferably dimensionally stable.
  • paper paper laminated with plastic (for example, polyethylene, polypropylene, polystyrene, etc.), glass substrate, and the like.
  • Metal plates eg, aluminum, zinc, copper, etc.
  • plastic films eg, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate , Polyvinyl acetal, polyimide, polyetherimide, epoxy resin (which may have SiO2, SiON, or ITO), bismaleimide resin, bismaleimide triazine resin, polyphenylene oxide, liquid Polymer, polytetrafluoroethylene, cyanate resin, etc., phenol resin, aramid resin, cycloolefin polymer, polyphenylene ether, benzocyclobutene resin, polyethersulfone, polyarylate), paper or plastic film on which metal is laminated or deposited included.
  • an epoxy resin or a polyimide resin is preferable.
  • a plate-like substrate (various substrates) is used as the substrate, but the substrate is not necessarily limited to a plate-like substrate, and a substrate having an arbitrary shape such as a cylindrical shape may be used. .
  • the latex used for the adhesion auxiliary layer contains at least one dispersant selected from an anionic dispersant and a nonionic dispersant, resin particles, and an aqueous dispersion medium.
  • the latex in the present invention is one in which resin particles insoluble in water are dispersed in water or a water-soluble dispersion medium, and contains an anionic dispersant or a nonionic dispersant.
  • the aqueous dispersion medium is water or a mixed solvent obtained by mixing water with a water-miscible organic solvent of 90% by mass or less.
  • water miscible organic solvents include water-soluble flammable liquids such as ketone solvents, ester solvents, alcohol solvents, ether solvents, glycol solvents, amine solvents, thiol solvents, and halogen solvents. Can be mentioned.
  • Water-soluble flammable liquid used for the aqueous dispersion medium will be described.
  • ketone solvent examples include 4-hydroxy-4-methyl-2-pentanone, ⁇ -butyrolactone, and hydroxyacetone.
  • Ester solvents include 2- (2-ethoxyethoxy) ethyl acetate, ethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, methyl cellosolve acetate, 2-hydroxyethyl acrylate, hydroxypropyl acrylate, methyl glycolate, glycol Examples include ethyl acid.
  • Alcohol solvents include methanol, ethanol, propanol, 1-methoxy-2-propanol, isopropyl alcohol, normal propyl alcohol, 3-acetyl-1-propanol, 2- (allyloxy) ethanol, 1-pentanol, 3-methyl- 1-butanol, n-hexanol, 1-heptanol, 2-ethyl-1,3-hexanediol, 2-aminoethanol, 2-amino-2-methyl-1-propanol, ( ⁇ ) -2-amino-1- Propanol, 3-amino-1-propanol, 2-dimethylaminoethanol, 2,3-epoxy-1-propanol, ethylene glycol, 2-fluoroethanol, diacetone alcohol, 2-methylcyclohexanol, 4-hydroxy-4- Methyl-2-pentano Glycerin, 2,2 ′, 2 ′′ -nitrilotriethanol, 2-pyridinemethanol, 2,2,3,3-
  • ether solvents include bis (2-ethoxyethyl) ether, bis [2- (2-hydroxyethoxy) ethyl] ether, 1,2-bis (2-methoxyethoxy) ethane, and bis [2- (2-methoxy).
  • Ethoxy) ethyl] ether bis (2-methoxyethyl) ether, 2- (2-butoxyethoxy) ethanol, 2- [2- (2-chloroethoxy) ethoxy] ethanol, 2-ethoxyethanol, 2- (2- Ethoxyethoxy) ethanol, 2-isobutoxyethanol, 2-2-isobutoxyethoxy) ethanol, 2-isopropoxyethanol, 2- [2- (2-methoxyethoxy) ethoxy] ethanol, 2- (2-methoxyethoxy) Ethanol, 1-ethoxy-2-propanol, 1-methoxy-2-propanol Tripropylene glycol monomethyl ether, methoxy acetic acid and 2-methoxy ethanol.
  • glycol solvents examples include diethylene glycol, triethylene glycol, ethylene glycol, hexaethylene glycol, propylene glycol, dipropylene glycol, and tripropylene glycol.
  • amine solvent examples include N-methyl-2-pyrrolidone and N, N-dimethylformamide.
  • thiol solvent examples include mercaptoacetic acid and 2-meltcaptoethanol.
  • halogen solvent examples include 3-bromobenzyl alcohol, 2-chloroethanol, 3-chloro-1,2-propanediol and the like.
  • Examples of the solvent included in the water-soluble flammable liquid other than the above solvents include methyl lactate, ethyl lactate, morpholine, N-ethylmorpholine, formic acid, acetic acid and the like.
  • the total content of the water-soluble flammable liquid contained in the mixed solvent is within the above range, only one kind may be used, or two or more kinds may be mixed and used.
  • the resin constituting the resin particles contained in the latex is not particularly limited.
  • the latex those containing resin particles containing a cyano group are particularly preferable.
  • Nipol 1561 (Nippon Zeon Corporation), Nipol 1562 (Nippon Zeon Corporation), Nipol 1577K (Nippon Zeon Corporation), Nipol LX110 (Nippon Zeon Corporation), LX 531 (Nippon Zeon Corporation), LX 531B (Nippon Zeon Corporation), Nipol SX1503A (Nippon Zeon Corporation), LX 513 (Nippon Zeon Corporation), Commercially available products such as NK-300 (Nippon A & L Co., Ltd.) and NK-301 (Nippon A & L Co., Ltd.) may be used.
  • These commercially available latexes contain an anionic dispersant and / or a nonionic dispersant as described below.
  • resin particles may be used in combination.
  • resin particles that can be used in combination include SBR and NR, IR and NR, CR and NR, NBR with different nitrile amounts, SBR with different styrene amounts, SBR and VP, NBR and MBR, SBR and NBR, and SBR. And MBR, BR and CR, NBR and VP, CR and VP, and the like.
  • the anionic dispersant or nonionic dispersant contained in the latex will be described.
  • Anionic dispersants include, for example, beef tallow fatty acids, partially hydrogenated beef tallow fatty acids, fatty acids such as oleic acid, palmitic acid, dodecyl sulfate, and fatty acid salts thereof, such as potassium salts and sodium salts; rosin acid, hydrogenated rosin acid, etc.
  • resin acid salts such as resin acids and sodium salts and potassium salts thereof
  • alkylbenzene sulfonic acids such as dodecylbenzene sulfonic acid and sodium salts thereof.
  • anionic dispersants long chain fatty acids such as oleic acid and palmitic acid and salts thereof are preferable from the viewpoint of ease of use.
  • Nonionic dispersants include polyethylene glycol ester type and pluronic type dispersants such as block copolymers of ethylene oxide and propylene oxide, and ethylene glycol type dispersants are preferred.
  • anionic dispersant or nonionic dispersant Only one type of anionic dispersant or nonionic dispersant may be used, or two or more types may be used in combination. Moreover, as a combination aspect of these dispersants, an aspect in which only two or more anionic dispersants are used, an aspect in which only two or more nonionic dispersants are used, one type or two or more types of anionic dispersant and one type Or any of the aspects using 2 or more types of nonionic dispersing agents may be sufficient. When used in combination, it is particularly preferable to use a combination of a long-chain fatty acid and a salt thereof as the anionic dispersant and an ethylene glycol type dispersant as the nonionic dispersant.
  • the film thickness of the resin layer A formed by the contact between the base material and the latex can be appropriately set, but is preferably 0.01 to 5 micrometers, preferably 0.06 to 3 micrometers. Is more preferable, and most preferably 1 micrometer or more and 2 micrometers or less.
  • the catalyst-supporting polymer liquid for plating applied to the wiring structure manufacturing method (apparatus) according to the present invention contains a polymer having a predetermined functional group and a solvent having a predetermined boiling point.
  • the solvent has a predetermined boiling point, an ink exhibiting excellent continuous ejection stability and pattern formability can be obtained.
  • the polymer used in the catalyst-supporting polymer solution for plating of the present invention is composed of a functional group that interacts with the electroless plating catalyst or its precursor (hereinafter also referred to as “interactive group” as appropriate) and a polymerizable functional group. And a polymer containing By including an interactive group in the polymer, excellent adsorptivity to a plating catalyst described later is achieved, and as a result, a plating film (metal film) having a sufficient thickness can be obtained during the plating process.
  • the polymerizable functional group is contained in the polymer, excellent adhesion to the substrate described later is exhibited, and a polymer layer having excellent strength can be obtained because a crosslinking reaction proceeds in the film.
  • the type of the interactive group is not particularly limited as long as it interacts with a plating catalyst described later.
  • non-dissociative functional groups such as polar groups (hydrophilic groups), groups capable of forming multidentate coordination, nitrogen-containing functional groups, sulfur-containing functional groups, oxygen-containing functional groups (functions that do not generate protons by dissociation) Group).
  • polar groups hydrophilic groups
  • sulfur-containing functional groups groups capable of forming multidentate coordination
  • nitrogen-containing functional groups nitrogen-containing functional groups
  • sulfur-containing functional groups sulfur-containing functional groups
  • oxygen-containing functional groups functions that do not generate protons by dissociation
  • polar groups include positively charged functional groups such as ammonium and phosphonium, sulfonic acid groups, carboxyl groups, phosphoric acid groups, phosphonic acid groups, groups containing an N-hydroxy structure, phenolic hydroxyl groups, hydroxyl groups, and the like.
  • Examples thereof include an acidic group having a negative charge or capable of dissociating into a negative charge. They adsorb with metal ions either in the form of a counter ion of the dissociating group or in a non-dissociated state.
  • the non-dissociable functional group is preferably a group capable of forming a coordination with a metal ion, a nitrogen-containing functional group, a sulfur-containing functional group, an oxygen-containing functional group, a phosphorus-containing functional group, or the like.
  • imide group pyridine group, tertiary amino group, ammonium group, pyrrolidone group, amidino group, triazine ring, triazole ring, benzotriazole group, benzimidazole group, quinoline group, pyrimidine group, pyrazine group, Quinazoline group, quinoxaline group, purine group, triazine group, piperidine group, piperazine group, pyrrolidine group, pyrazole group, aniline group, group containing alkylamine group structure, group containing isocyanuric structure, nitro group, nitroso group, azo group, Nitrogen-containing functional groups such as diazo group, azide group, cyano group, cyanate group (R—O—CN), ether group, carbonyl group, ester group, group containing N-oxide structure, group containing S-oxide structure, etc.
  • an imidazole group, a urea group, or a thiourea group may be used as long as it is non-dissociative due to a relationship with an adjacent atom or atomic group.
  • it may be a functional group derived from a compound having an inclusion ability such as cyclodextrin and crown ether.
  • n is an integer of 1 to 5
  • Structure or a cyano group is particularly preferable, and a cyano group is more preferable.
  • Examples of the polymerizable group include a radical polymerizable group and a cationic polymerizable group. From the viewpoint of reactivity with the substrate described later, a radical polymerizable group is preferable.
  • Examples of the radical polymerizable group include unsaturated carboxylic acid ester groups such as acrylic acid ester groups, methacrylic acid ester groups, itaconic acid ester groups, crotonic acid ester groups, isocrotonic acid ester groups, maleic acid ester groups, styryl groups, Examples include allyl group.
  • a methacrylic acid ester group (methacryloyl group), an acrylic acid ester group (acryloyl group), an allyl group, and a styryl group are preferable, and an acryloyl group and a methacryloyl group are particularly preferable.
  • One preferred embodiment of the polymer is a polymer containing a unit (repeating unit) represented by the following formula (1) because it is more excellent in reactivity with the substrate.
  • the unit is a unit having a polymerizable group (polymerizable group-containing unit).
  • R 1 to R 4 each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group.
  • R 1 to R 4 are a substituted or unsubstituted alkyl group, an alkyl group having 1 to 4 carbon atoms is preferable, and an alkyl group having 1 to 2 carbon atoms is more preferable.
  • examples of the unsubstituted alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group
  • examples of the substituted alkyl group include a methoxy group, a hydroxy group, and a halogen atom (for example, a chlorine atom).
  • a bromine atom, a fluorine atom) and the like and a methyl group, an ethyl group, a propyl group and a butyl group.
  • R 1 is preferably a hydrogen atom, a methyl group, or a methyl group substituted with a hydroxy group or a bromine atom.
  • R 2 is preferably a hydrogen atom, a methyl group, or a methyl group substituted with a hydroxy group or a bromine atom.
  • R 3 is preferably a hydrogen atom.
  • R 4 is preferably a hydrogen atom.
  • Y and Z each independently represent a single bond or a substituted or unsubstituted divalent organic group.
  • the divalent organic group include a substituted or unsubstituted aliphatic hydrocarbon group (preferably having 1 to 11 carbon atoms), a substituted or unsubstituted aromatic hydrocarbon group (preferably having 6 to 12 carbon atoms), —O —, —S—, —N (R) — (R: alkyl group), —CO—, —NH—, —COO—, —CONH—, or a combination thereof (eg, alkyleneoxy group, alkylene group) Oxycarbonyl group, alkylenecarbonyloxy group, etc.).
  • the organic group may have a substituent such as a hydroxy group as long as the effects of the invention are not impaired.
  • Examples of the substituted or unsubstituted aliphatic hydrocarbon group include a methylene group, an ethylene group, a propylene group, a butylene group, a pentyl group, a hexyl group, or a group such as a methoxy group, a hydroxy group, or a halogen atom (for example, a chlorine atom). , Bromine atom, fluorine atom) and the like.
  • the substituted or unsubstituted aromatic hydrocarbon group is preferably an unsubstituted phenyl group or a phenyl group substituted with a methoxy group, a hydroxy group, a halogen atom (for example, a chlorine atom, a bromine atom, or a fluorine atom). .
  • Y and Z are preferably an ester group (—COO—), an amide group (—CONH—), an ether group (—O—), a substituted or unsubstituted aromatic hydrocarbon group, and the like.
  • L 1 represents a substituted or unsubstituted divalent organic group.
  • the definition of the divalent organic group is synonymous with the organic group represented by the above Y and Z.
  • a substituted or unsubstituted aliphatic hydrocarbon group a substituted or unsubstituted aromatic hydrocarbon group, —O —, —S—, —N (R) — (R: alkyl group), —CO—, —NH—, —COO—, —CONH—, or a combination thereof may be mentioned.
  • L 1 is preferably an unsubstituted alkyl group or a divalent organic group having a urethane bond or a urea bond, more preferably a divalent organic group having an unsubstituted alkyl group and a urethane bond, and the total number of carbon atoms. Those having 1 to 9 are particularly preferred. Incidentally, the total number of carbon atoms of L 1, means the total number of carbon atoms contained in the substituted or unsubstituted divalent organic group represented by L 1.
  • L 1 is preferably a structure represented by the following formula (1-1), the following formula (1-2), or the following formula (1-3).
  • R a and R b are each independently two or more atoms selected from the group consisting of a carbon atom, a hydrogen atom, and an oxygen atom. It is a divalent organic group formed using Preferably, it is a substituted or unsubstituted methylene group, ethylene group, propylene group or butylene group, ethylene oxide group, diethylene oxide group, triethylene oxide group, tetraethylene oxide group, dipropylene oxide group, tripropylene oxide group, tetrapropylene. An oxide group is mentioned.
  • a preferred embodiment of the unit represented by the above formula (1) is a unit represented by the following formula (4).
  • R 1, R2, Z and L 1 are the same as the definition of each group in the unit represented by the above formula (1).
  • T represents an oxygen atom or NR (R represents a hydrogen atom or an alkyl group, preferably a hydrogen atom or an unsubstituted alkyl group having 1 to 5 carbon atoms).
  • a preferred embodiment of the unit represented by the above formula (4) is a unit represented by the following formula (5).
  • R ⁇ 1 >, R ⁇ 2 > and L ⁇ 1 > are the same as the definition of each group in the unit represented by the said Formula (1).
  • T and Q each independently represent an oxygen atom or NR (R represents a hydrogen atom or an alkyl group, preferably a hydrogen atom or an unsubstituted alkyl group having 1 to 5 carbon atoms).
  • W is preferably an oxygen atom.
  • L 1 is preferably an unsubstituted alkylene group or a divalent organic group having a urethane bond or a urea bond, and a divalent organic group having a urethane bond.
  • a group having a total number of carbon atoms of 1 to 9 is particularly preferable.
  • the content of the unit represented by the above formula (1) in the polymer is not particularly limited. However, from the viewpoints of adhesion to a substrate described later, storage stability, and difficulty in synthesis, all units (100 mol%) are used. On the other hand, 5 mol% or more and 50 mol% or less are preferable, and 5 mol% or more and 40 mol% or less are more preferable.
  • the amount is less than 5 mol%, the reactivity (curability and polymerizability) may be lowered.
  • the amount exceeds 50 mol%, gelation is likely to occur during the synthesis of the polymer, and the control of the reaction becomes difficult.
  • One preferred embodiment of the polymer includes a polymer having a unit (repeating unit) represented by the following formula (2) from the viewpoint of the excellent adsorptivity of the plating catalyst.
  • the unit is a unit containing an interactive group (interactive group-containing unit).
  • R 5 represents a hydrogen atom or a substituted or unsubstituted alkyl group.
  • the substituted or unsubstituted alkyl group represented by R 5 has the same meaning as the substituted or unsubstituted alkyl group represented by R 1 to R 4 described above.
  • R 5 is preferably a hydrogen atom, a methyl group, or a methyl group substituted with a hydroxy group or a bromine atom.
  • X and L 2 each independently represent a single bond or a substituted or unsubstituted divalent organic group.
  • the definition of the divalent organic group is as described above.
  • X is preferably a single bond, an ester group, an amide group or an ether group, more preferably a single bond, an ester group or an amide group, and most preferably a single bond or an ester group.
  • L 2 is one of the preferred embodiments that is a linear, branched, or cyclic alkylene group, an aromatic group, or a combination thereof.
  • the group obtained by combining the alkylene group and the aromatic group may further contain an ether group, an ester group, an amide group, a urethane group, or a urea group.
  • L 2 preferably has a total carbon number of 1 to 15, and is particularly preferably unsubstituted.
  • the total number of carbon atoms for example, means the total number of carbon atoms contained in the substituted or unsubstituted divalent organic group represented by L 2.
  • a methylene group an ethylene group, a propylene group, a butylene group, a phenylene group, and those groups substituted with a methoxy group, a hydroxyl group, a chlorine atom, a bromine atom, a fluorine atom, etc., The group which combined these is mentioned.
  • W represents a non-dissociable functional group that interacts with the plating catalyst or its precursor.
  • W may be bonded directly from the polymer straight chain. That is, the aforementioned X and L 2 may be a single bond, and W may be directly bonded to a carbon atom.
  • the definition of the non-dissociable functional group is as described above.
  • R ⁇ 5 >, X and L ⁇ 2 > is synonymous with each group in the said Formula (2).
  • Another preferred embodiment of the unit represented by the above formula (2) is a unit represented by the following formula (7).
  • R 5 and L 2 are as defined each group in the above formula (2).
  • R 6 represents an unsubstituted alkyl group, alkenyl group, alkynyl group, or aryl group.
  • the content of the unit represented by the above formula (2) in the polymer is not particularly limited, but from the viewpoint of adsorbability to the plating catalyst or its precursor and ease of synthesis, all units (100 mol%) in the polymer ) To 20 mol% to 90 mol%, more preferably 30 mol% to 80 mol%.
  • the polymer may further have a unit represented by the following formula (3) from the viewpoint that the affinity for an aqueous solution is improved and the developability is further improved.
  • the unit corresponds to a unit having an ionic polar group.
  • R 7 represents a hydrogen atom or a substituted or unsubstituted alkyl group.
  • the substituted or unsubstituted alkyl group represented by R 7 has the same meaning as the substituted or unsubstituted alkyl group represented by R 1 to R 4 described above.
  • R 7 is preferably a hydrogen atom, a methyl group, or a methyl group substituted with a hydroxy group or a bromine atom.
  • U and L 3 each independently represent a single bond or a substituted or unsubstituted divalent organic group. The definition of the divalent organic group is as described above.
  • the preferred embodiment of U is the same as the preferred embodiment of X above.
  • a preferred embodiment of L 3 is the same as the preferred embodiment of L 2 described above.
  • V represents an ionic polar group and is not particularly limited as long as it can impart developability to a polymer aqueous solution. Specific examples include a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, and a boronic acid group.
  • a carboxylic acid group is preferable, and in particular, it is bonded directly to the polymer main chain from the viewpoint of achieving both low water absorption necessary for electrical wiring.
  • Carboxylic acid groups, carboxylic acid groups directly bonded to the alicyclic structure (alicyclic carboxylic acid groups), carboxylic acid groups separated from the polymer main chain (long chain carboxylic acid groups) are preferred, most preferably It is a carboxylic acid group directly connected to the polymer main chain.
  • Such an ionic polar group may be introduced into the polymer by addition / substitution to a part of the polymer, or by copolymerizing a monomer in which the ionic polar group is pendant, It may be introduced into the polymer.
  • the unit represented by the above formula (3) is moderately acidic (does not decompose other functional groups), exhibits hydrophilicity in an alkaline aqueous solution, and exhibits hydrophobicity due to the cyclic structure when water is dried.
  • V is a carboxylic acid group, and it is preferable that L 3 has a 4-membered to 8-membered ring structure at the connecting portion with V.
  • examples of the 4- to 8-membered ring structure include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a phenyl group, and among them, a cyclohexyl group and a phenyl group are preferable. That is, in this embodiment, the terminal of the unit represented by the above formula (3) is an alicyclic carboxylic acid group.
  • the unit represented by the above formula (3) is moderately acidic (does not decompose other functional groups), shows hydrophilicity in an alkaline aqueous solution, and becomes hydrophobic due to the long-chain alkyl group structure when water is dried. From the viewpoint that it is easy to show, it is preferable that V is a carboxylic acid group and the chain length of L 3 is 6 to 18 atoms.
  • the chain length of L 3 represents the distance between U and V in the above formula (3), and it is preferable that the distance between U and V is in the range of 6 to 18 atoms. Means.
  • the chain length of L 3 is more preferably 6 to 14 atoms, and still more preferably 6 to 12 atoms.
  • V is a carboxylic acid group and U and L 3 are single bonds.
  • the carboxylic acid group is shielded by the polymer main chain, and as a result, it can be hydrophobized, and immediately after the metal pattern is formed, the adhesion between the substrate and the metal pattern can be improved.
  • the water resistance of the polymer layer can be increased.
  • the content of the unit represented by the above formula (3) in the polymer is not particularly limited, but it is 20 moles with respect to all units (100 mole%) in the polymer from the viewpoint of developability with an aqueous solution and moisture-resistant adhesion. % To 70 mol%, more preferably 20 mol% to 60 mol%.
  • it is 30 mol% or more and 50 mol% or less. Within this range, both developability and moisture-resistant adhesion can be achieved.
  • each unit may be a random polymer bonded at random, or each unit may be a block polymer that is connected to the same type to form a block portion. Good.
  • the polymer described above may contain other units in addition to the above units as long as the effects of the present invention are not impaired.
  • a polymerizable group is introduced by reacting with a polymer, a small amount of a reactive portion remains when it is difficult to introduce 100%, so this may become another unit. There is also sex.
  • a polymer having a unit represented by the above formula (1) and a unit represented by the above formula (6), and the above formula (1) A polymer having a unit represented by formula (7) and a unit represented by formula (7), a unit represented by formula (1), a unit represented by formula (2), and a formula (3). And a polymer having a unit to be prepared.
  • the weight average molecular weight of the catalyst-supporting polymer for plating applied in this example is preferably 20000 or less from the viewpoint of forming a fine pattern.
  • the polymerization degree of the catalyst-supporting polymer for plating applied in this example is preferably a 10-mer or more, and more preferably a 20-mer or more. Moreover, 2000-mer or less is preferable and 1000-mer or less is particularly preferable.
  • Polymer synthesis method As a polymer synthesis method, the following methods are preferably exemplified.
  • preferred methods are the methods ii) and iii).
  • the kind of the polymerization reaction at the time of synthesis is not particularly limited, and includes radical polymerization, cationic polymerization, anionic polymerization, etc., but it is preferable to carry out by radical polymerization.
  • the monomer which has an ionic polar group is used together.
  • the polymer of the present invention can be synthesized with reference to the method described in paragraphs [0097] to [0125] of JP2009-280905A. Specifically, in the synthesis method of ii) above, in order to convert a double bond precursor to a double bond, the leaving groups represented by B and C are removed by elimination reaction as shown below. A method in which C is extracted by the action of a base and B is eliminated.
  • A is an organic group having a polymerizable group
  • R1 to R3 are each independently a hydrogen atom or a monovalent organic group
  • B and C are each independently removed by an elimination reaction. It is a leaving group
  • one of B and C is a hydrogen atom
  • the other represents a halogen atom, a sulfonate group, an ether group, or a thioether group.
  • the elimination reaction here means that C is extracted by the action of a base and B is eliminated.
  • B is preferably eliminated as an anion and C as a cation.
  • Preferred examples of the base include hydrides of alkali metals, hydroxides or carbonates, organic amino compounds, and metal alkoxide compounds.
  • examples of the monomer having a reactive group for introducing a double bond include a monomer having a carboxyl group, a hydroxyl group, an epoxy group, or an isocyanate group as a reactive group.
  • the monomer having a polymerizable group to be reacted with a polymer having a reactive group preferably has a reactive group such as a carboxyl group, a hydroxyl group, an epoxy group, an isocyanate group, or a halogenated benzyl group.
  • (polymer reactive group, monomer reactive group) (carboxyl group, epoxy group), (carboxyl group, isocyanate group), (hydroxyl group, epoxy group), (hydroxyl group, isocyanate group), (isocyanate group, (Hydroxyl group), (isocyanate group, carboxyl group), (epoxy group, carboxyl group) and the like.
  • a polymer having a hydroxyl group in a side chain and a compound having an isocyanate group and a polymerizable group are used, and the urethane group in L 1 is added to the hydroxyl group by adding the isocyanate group. Is preferably formed.
  • a polymer having a carboxyl group in a side chain and a compound having a benzyl halide group and a polymerizable group are used, and the benzyl halide group is added to the carboxyl group to thereby add L 1 It is also preferred to form a methylene group therein.
  • the inkjet ink of the present invention contains solvents (liquids) that satisfy the average boiling point represented by the following formula (A).
  • the solvent can dissolve or disperse the above-described polymer.
  • the solvent used has a predetermined boiling point, it is possible to obtain an ink that exhibits excellent continuous ejection stability and excellent formability of the polymer layer.
  • T bi represents the boiling point (° C.) (under 1 atm) of the i-th solvent in the inkjet ink.
  • i represents an integer of 1 to n.
  • N represents the number of solvents contained in the inkjet ink, and specifically, n represents an integer of 1 or more.
  • the upper limit of n is not particularly limited, but is preferably 5 or less and more preferably 3 or less from the viewpoint of cost.
  • ⁇ represents the total.
  • n 1, and the boiling point value of the solvent used corresponds to T (b) .
  • T (b) ⁇ T X ⁇ (mass of solvent X / Total solvent mass) ⁇ + ⁇ T Y ⁇ (mass of solvent Y / total mass of solvent) ⁇ It can be obtained more.
  • T (b) ⁇ T X ⁇ (mass of solvent X / total mass of solvent) ⁇ + ⁇ T Y ⁇ (mass of solvent Y / total mass of solvent) ⁇ + ⁇ T Z ⁇ (mass of solvent Z / total mass of solvent) ⁇ It can be obtained more.
  • the solvent used may be a non-polymerizable solvent (non-polymerizable liquid) or a polymerizable solvent containing a polymerizable group (polymerizable liquid).
  • the polymerizable solvent means a liquid monomer having a polymerizable group.
  • the polymerizable solvent is not particularly limited as long as it has a dischargeable viscosity. From the viewpoint of solubility, a polymerizable solvent having a molecular weight of 300 or less and a polymerizable functional group number of 2 or less is particularly preferable.
  • examples of the solvent used include aldehyde solvents (for example, 2-alaldehyde, benzaldehyde, etc.), ether solvents (for example, ethylene glycol dimethyl ether, propyl ether, 1,4-dioxane, propylene glycol).
  • aldehyde solvents for example, 2-alaldehyde, benzaldehyde, etc.
  • ether solvents for example, ethylene glycol dimethyl ether, propyl ether, 1,4-dioxane, propylene glycol.
  • Amide solvents for example, N, N-dimethylformua) N, N-dimethylacetamide, N-methylformamide, N-methylacetamide, 1-methyl-2-pyrrolidone, etc.
  • amine solvents for example, triethylamine, pyridine, etc.
  • aliphatic hydrocarbon solvents for example, Cyclohexane, heptane, etc.
  • aromatic hydrocarbon solvents eg, benzene, toluene, xylene, aniline, cresol, tetralin
  • alcohol solvents eg, ethanol, butanol, hexanol, methylcyclohexanol, glycerol, 2-ethyl- 1-hexanol, benzyl alcohol, decanol, etc.
  • ester solvents eg, ethyl acetate, propyl acetate, diethyl carbonate, ethyl lactate, 2-ethoxye
  • alcohol solvents especially, (oligo) ethylene glycol derivatives, (oligo) propylene glycol derivatives), polymerizable solvents Etc. are preferable.
  • the solvent applied to the catalyst-supporting polymer liquid for plating shown in this example is used as a mixed solvent of two or more kinds having different boiling points among those described above.
  • the boiling point of each solvent is a boiling point represented by the following formula (B) or the following formula (C), respectively.
  • W Ai represents a mass ratio (i-th solvent A mass / total solvent A mass) (mass fraction) to the total amount of the solvent A of the i-th solvent A in the inkjet ink.
  • T Abi represents the boiling point (° C.) (under 1 atm) of the i-th solvent A in the inkjet ink.
  • i represents an integer of from 1 n A.
  • W Bi represents a mass ratio (i-th solvent B mass / total solvent B mass) (mass fraction) to the total amount of the solvent B of the i-th solvent B in the inkjet ink.
  • T Bbi represents the boiling point (° C.) (under 1 atm) of the i-th solvent B in the inkjet ink.
  • i represents an integer from 1 to n B.
  • n B represents the number of the solvent B contained in the inkjet ink. Specifically, n B represents an integer of 1 or more.
  • the upper limit of nB is not particularly limited, but is preferably 5 or less and more preferably 3 or less from the viewpoint of cost and the like.
  • the solvent A contains more solvent A than solvent B on a mass basis in the inkjet.
  • the mass ratio between the solvent A and the solvent B in the inkjet ink is a numerical value exceeding 1.
  • the mass ratio is more preferably 2 or more from the viewpoint of both continuous discharge stability and the surface state of the polymer film during drawing.
  • 20 or less is usually preferable and 10 or less is more preferable.
  • a preferable embodiment of the solvent B includes a polymerizable solvent (polymerizable liquid) from the viewpoint of improving the surface condition of the polymer film at the time of drawing.
  • a solvent having a relatively low molecular weight and a high solubility in the polymer component preferably a molecular weight of 300 or less and a bifunctional or less, is preferable, and further, a non-dissociative function that forms an interaction with the plating catalyst or its precursor. It preferably has a group (W group in formula (1)).
  • imide group pyridine group, tertiary amino group, ammonium group, pyrrolidone group, amidino group, triazine ring, triazole ring, benzotriazole group, benzimidazole group, quinoline group, pyrimidine group, pyrazine group, solooline Group, quinoxaline group, purine group, triazine group, piperidine group, piperazine group, pyrrolidine group, pyrazole group, aniline group, group containing alkylamine group structure, group containing isocyanuric structure, nitro group, nitroso group, azo group, diazo Group, azide group, cyano group, nitrogen-containing functional group such as cyanate group (R—O—CN), ether group, carbonyl group, ester group, group containing N-oxide structure, group containing S-oxide structure, N -(Meth) acrylates containing groups containing hydroxy structures, phenolic hydroxyl groups, or
  • the catalyst-supporting polymer liquid for plating applied to the present invention contains the polymer and the solvent.
  • the content of the polymer in the inkjet ink is not particularly limited, but is preferably 1% by mass or more and 20% by mass or less, more preferably 4% by mass or more and 15% by mass or less with respect to the total amount of the ink in terms of excellent continuous discharge stability. preferable.
  • the content of the solvent in the inkjet ink is not particularly limited, but is preferably 80% by mass or more and 99% by mass or less, and more preferably 85% by mass or more and 96% by mass or less with respect to the total amount of the ink in terms of excellent continuous discharge stability. More preferred.
  • the catalyst-supporting polymer liquid for plating applied to the present invention may contain a surfactant, a radical generator and the like as long as the effects of the present invention are not impaired.
  • the catalyst-supporting polymer liquid for plating applied to the present invention may further contain a surfactant.
  • a surfactant it is preferable in terms of inkjet discharge stability and leveling properties upon landing.
  • surfactant examples include nonionic surfactants, amphoteric surfactants, anionic surfactants having ammonium ions as counterions, and cationic surfactants having organic acid anions as counterions.
  • nonionic surfactants examples include polyethylene glycol derivatives and polypropylene glycol derivatives.
  • amphoteric surfactants include long-chain alkyl betaines.
  • anionic surfactant having an ammonium ion as a counter ion examples include, for example, a long-chain alkyl sulfate ammonium salt, an alkyl aryl sulfate ammonium salt, an alkyl aryl sulfonate ammonium salt, an alkyl phosphate ammonium salt, and an ammonium salt of a polycarboxylic acid polymer.
  • a long-chain alkyl sulfate ammonium salt an alkyl aryl sulfate ammonium salt
  • an alkyl aryl sulfonate ammonium salt an alkyl phosphate ammonium salt
  • an ammonium salt of a polycarboxylic acid polymer examples include, for example, a long-chain alkyl sulfate ammonium salt, an alkyl aryl sulfate ammonium salt, an alkyl aryl sulfonate ammonium salt, an alky
  • the content of the surfactant in the catalyst-supporting polymer liquid for plating is not particularly limited, but is preferably 5% by mass or less, and more preferably 0.01% by mass or more and 2% by mass or less with respect to the total amount of the ink. If it is in the said range, it is preferable at the point which can obtain preferable surface tension, without impairing the other physical property of an ink.
  • the catalyst-supporting polymer solution for plating applied to the present invention may contain a radical generator (polymerization initiator) for the purpose of promoting the reaction of the polymerizable group in the polymer.
  • the radical generator can be selected according to the type of polymer, and examples thereof include a photo radical generator and a thermal radical generator.
  • At least one selected from the group consisting of oxime esters, acylphosphine oxides, ⁇ -hydroxyalkyl ketones, lophine dimers, and trihalomethyltriazines is preferable.
  • the content of the radical generator is preferably 0.1% by mass or more and 5% by mass or less, and more preferably 0.5% by mass or more and 3% by mass or less with respect to the total amount of the ink. When the content is in the above-described range, a better sensitivity and a strong cured portion can be formed.
  • a known inkjet ink production method can be applied to the production of the catalyst-supporting polymer liquid for plating applied to the present invention. For example, after dissolving the polymer in a solvent, each component (for example, a surfactant and a radical generator) necessary for the inkjet ink can be dissolved to prepare the inkjet ink.
  • each component for example, a surfactant and a radical generator
  • the physical property value of the ink-jet ink of the present invention is not particularly limited as long as it can be ejected by the ink-jet head, but the ink viscosity is 20 millipascal seconds or less at the temperature in the head at the time of ejection from the viewpoint of stable ejection. Preferably, it is 2 millipascal seconds or more and 15 millipascal seconds or less. Further, when ejected by the apparatus, the temperature of the ink-jet ink is preferably maintained at a substantially constant temperature in the range of 20 ° C. or more and 80 ° C. or less, and the viscosity is more preferably 20 millipascal seconds in the temperature range. .
  • the viscosity of the ink decreases, and it becomes possible to eject higher viscosity ink.
  • the temperature is increased, the ink is denatured by heat and a thermal polymerization reaction occurs in the head, or the solvent is evaporated on the surface of the nozzle that ejects the ink, so that nozzle clogging is likely to occur. It is preferable that it is below °C.
  • the viscosity is a value measured by using a commonly used E-type viscometer (for example, an E-type viscometer manufactured by Toki Sangyo Co., Ltd. (RE-80L)).
  • the surface tension (static surface tension) at 25 ° C. of the ink-jet ink is 20 millinewtons per meter or more and 40 millinewtons per meter in terms of improvement in wettability with respect to a non-permeable substrate and ejection stability. Preferably, it is more preferably 20 millinewtons per meter or more and 35 millinewtons per meter or less.
  • the above-described surface tension is measured by a Wilhelmy method using a commonly used surface tension meter (for example, Kyowa Interface Science Co., Ltd., surface tension meter FACE SURFACE TENSIOMETER CBVB-A3, etc.) at a liquid temperature of 25 ° C. and 60%. It is a value measured by RH.
  • a commonly used surface tension meter for example, Kyowa Interface Science Co., Ltd., surface tension meter FACE SURFACE TENSIOMETER CBVB-A3, etc.
  • plating catalyst-carrying polymer (plating catalyst-carrying polymer liquid) described above is not intended to limit the scope of application of the present invention, and can be appropriately changed within the range where the effects of the present invention can be obtained.
  • a method and an apparatus for drawing a wiring pattern on a substrate have been illustrated.
  • the present invention can be applied to a form in which a pattern is formed on a resin-made housing and the production of a thin panel such as an organic EL panel. Thus, the same effect can be obtained.
  • (Invention 1) Functional liquid containing a catalyst-supporting polymer compound for plating, a high-boiling solvent having a boiling point of 190 ° C. or higher and lower than 240 ° C., and a low-boiling solvent having a boiling point of 75 ° C. or higher and lower than 105 ° C.
  • a functional liquid discharging step for discharging the liquid onto the substrate by an ink jet method based on predetermined discharge conditions, and heating the base material from the start of discharging the functional liquid to the end of discharging in the functional liquid discharging step.
  • a diameter D 1 when a droplet of a functional liquid in flight is regarded as a spherical shape, dot spacing W of the functional liquid to be formed, the diameter D 2 of the dots of the functional liquid that is formed on said substrate, D 1 ⁇ W ⁇ by satisfying the relation of D 2, such as bulges and jaggies Occurrence can be prevented.
  • the wetting and spreading of the functional liquid is suppressed by heating the base material while discharging the functional liquid.
  • Invention 2 In the functional liquid pattern forming method described in Invention 1, the molecular weight of the polymer compound is 50000 or less.
  • the molecular weight of the polymer compound is 20000 or less is more preferable.
  • the mass ratio of the polymer compound in the functional liquid is preferably 5% by mass or less.
  • invention 3 invention in the functional liquid pattern forming method as described in 1 or 2, wherein the functional liquid discharging step, the interval W of the dot of the functional liquid, the diameter D 2 of the dots of the functional liquid, based on the ejection conditions satisfying the following relationship W ⁇ D 2/2, to eject the functional liquid.
  • a fine pattern having a uniform pattern width can be formed.
  • invention 4 In the functional liquid pattern forming method according to any one of Inventions 1 to 3, the heating step heats the base material so that a surface temperature of the base material is 45 ° C. or higher. .
  • wetting and spreading of the functional liquid on the substrate can be prevented, and a preferable fine pattern can be formed.
  • an embodiment in which the surface temperature of the substrate is 60 ° C. or higher is preferable.
  • invention 5 The method for forming a functional liquid pattern according to any one of Inventions 1 to 4, further comprising an adhesion auxiliary layer forming step of forming an adhesion auxiliary layer on the substrate, wherein the functional liquid ejection step is an adhesion
  • the functional liquid is discharged onto the base material on which the auxiliary layer is formed.
  • the functional liquid ejection step includes stacking two or more layers of the functional liquid pattern, and the second and subsequent layers.
  • the functional liquid droplet diameter D 1 , the functional liquid dot interval W, and the functional liquid dot diameter D 2 satisfy the following relationship: D 1 ⁇ W ⁇ D 2
  • the functional liquid is ejected based on the satisfying ejection conditions.
  • a preferable fine laminated pattern can be formed without causing the pattern after the second layer to protrude from the pattern of the lower layer, and without causing bulge or jaggy in the pattern after the second layer.
  • the functional liquid discharge step is based on the same discharge conditions as the pattern formation of the first layer in the second and subsequent layer pattern formation.
  • the discharge conditions are optimized by sharing the discharge conditions for forming the first-layer pattern and the discharge conditions for forming the second and subsequent patterns.
  • a functional liquid containing a functional liquid on the base material by an ink jet method based on predetermined ejection conditions, and from the start of functional liquid ejection to the end of ejection in the functional liquid ejection process A heating step of heating the base material, a plating catalyst applying step of applying a plating catalyst or a plating catalyst precursor to the formed functional liquid pattern, and the plating catalyst or the plating catalyst precursor.
  • the following formula D 1 ⁇ W ⁇ is a state which satisfies the relation of D 2, the conductive pattern forming method.
  • invention 9 In the conductive pattern formation method according to Invention 8, in the functional liquid ejection step, the functional liquid pattern is laminated in two or more layers, and the pattern is formed in the second and subsequent layers. Based on the ejection conditions where the diameter D 1 of the functional liquid droplet, the interval W between the dots of the functional liquid, and the diameter D 2 of the functional liquid dots satisfy the relationship of the following formula D 1 ⁇ W ⁇ D 2 , The functional liquid is discharged.
  • a preferable conductive pattern in which the influence of the surface roughness of the substrate is eliminated can be formed by sufficiently increasing the thickness of the functional liquid pattern.
  • (Invention 10) Functional liquid containing a catalyst-supporting polymer compound for plating, a high-boiling solvent having a boiling point of 190 ° C. or higher and lower than 240 ° C., and a low-boiling solvent having a boiling point of 75 ° C. or higher and lower than 105 ° C.
  • An ink jet head for discharging the ink onto the substrate, a discharge control means for controlling the discharge of the ink jet head based on a predetermined discharge condition, and from the start of discharge of the functional liquid to the end of discharge in the functional liquid discharge step.
  • An inkjet head includes a nozzle that discharges a functional liquid, a liquid chamber that communicates with the nozzle and stores the functional liquid discharged from the nozzle, and a pressurizing unit that pressurizes the functional liquid in the liquid chamber There is an aspect provided with.
  • invention 11 In the functional liquid pattern formation system according to Invention 10, the discharge control unit stacks two or more layers of the functional liquid pattern, and in the pattern formation of the second and subsequent layers, the functionality
  • the diameter D 1 of the liquid droplet, the interval W between the functional liquid dots, and the diameter D 2 of the functional liquid dots are based on ejection conditions satisfying the relationship of the following formula D 1 ⁇ W ⁇ D 2 ,
  • the functional liquid pattern formation system of Claim 9 which controls discharge of an inkjet head.
  • An ink jet head for discharging the ink onto the substrate, a discharge control means for controlling the discharge of the ink jet head based on a predetermined discharge condition, and from the start of discharge of the functional liquid to the end of discharge in the functional liquid discharge step.
  • Plating means for applying a plating treatment to the pattern of the functional liquid, and the predetermined discharge condition is that the droplets of the functional liquid are spheres in flight.
  • the diameter D 1 of the when regarded as Jo, the distance W between the dots of the functional liquid that is formed on the substrate, and the diameter D 2 of the dots of the functional liquid that is formed on said substrate, the following is a state which satisfies the relationship of formula D 1 ⁇ W ⁇ D 2, conductive pattern forming system.
  • the ejection control unit In the conductive pattern formation system according to Invention 12, the ejection control unit stacks two or more layers of the functional liquid pattern, and the functional liquid is formed in pattern formation of the second and subsequent layers.
  • the droplet diameter D 1 , the functional liquid dot interval W, and the functional liquid dot diameter D 2 satisfy the following relationship: D 1 ⁇ W ⁇ D 2. Controls ejection of the head.
  • a heating step, a plating catalyst application step for applying a plating catalyst or a plating catalyst precursor to the formed functional liquid pattern, and a functional liquid pattern applied with the plating catalyst or the plating catalyst precursor. includes a plating step of performing plating processing, a predetermined discharge condition, the droplets of the functional liquid in the flight diameter D 1 of the when regarded as spherical, And distance W between the dots of the functional liquid that is formed on the substrate, and the diameter D 2 of the dots of the functional liquid that is formed on said substrate, the following relationship D 1 ⁇ W ⁇ D 2
  • the conductive pattern structure manufacturing method which is a state to satisfy

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Abstract

Un motif d'un liquide polymère de support de catalyseur pour un plaquage est formé par chauffage et maintien d'une matière de base à une température de surface de 45°C ou plus (de préférence 60°C ou plus) et éjection du liquide polymère de support de catalyseur pour le plaquage, qui contient un polymère de support de catalyseur pour le plaquage, un solvant à point d'ébullition élevé et un solvant à bas point d'ébullition sur la matière de base par un système à jet d'encre sur la base de conditions d'éjection dans lesquelles un diamètre D1 pour les gouttelettes éjectées, le pas W entre des points du liquide polymère de support de catalyseur pour le plaquage et le diamètre de point D2 pour le liquide satisfont la relation D1 < W < D2. De plus, après que le liquide a été durci, un motif conducteur qui est formé à partir d'un film de plaquage est formé par application du catalyseur de placage (ou du précurseur de catalyseur de plaquage) et réalisation d'un plaquage. Ainsi, un motif fin préféré peut être formé en évitant l'apparition de bombement ou de mouvement saccadé.
PCT/JP2012/065708 2011-06-24 2012-06-20 Procédé de formation de motif, système de formation de motif et procédé de fabrication d'une structure de motif WO2012176793A1 (fr)

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JP2011140729A JP2013008851A (ja) 2011-06-24 2011-06-24 機能性液体パターン形成方法、導電性パターン形成方法、機能性液体パターン形成システム、導電性パターン形成システム、機能性液体パターン構造体製造方法、及び導電性パターン構造体製造方法
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