WO2016009829A1 - Conductive film for touch panel sensor, touch panel sensor, and touch panel - Google Patents

Conductive film for touch panel sensor, touch panel sensor, and touch panel Download PDF

Info

Publication number
WO2016009829A1
WO2016009829A1 PCT/JP2015/068930 JP2015068930W WO2016009829A1 WO 2016009829 A1 WO2016009829 A1 WO 2016009829A1 JP 2015068930 W JP2015068930 W JP 2015068930W WO 2016009829 A1 WO2016009829 A1 WO 2016009829A1
Authority
WO
WIPO (PCT)
Prior art keywords
layer
group
touch panel
plated
patterned
Prior art date
Application number
PCT/JP2015/068930
Other languages
French (fr)
Japanese (ja)
Inventor
佐藤 真隆
Original Assignee
富士フイルム株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 富士フイルム株式会社 filed Critical 富士フイルム株式会社
Priority to JP2016534357A priority Critical patent/JP6279082B2/en
Priority to CN201580028793.0A priority patent/CN106462284B/en
Publication of WO2016009829A1 publication Critical patent/WO2016009829A1/en

Links

Images

Classifications

    • GPHYSICS
    • G06COMPUTING; CALCULATING OR COUNTING
    • G06FELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means

Definitions

  • the present invention relates to a conductive film for a touch panel sensor, a touch panel sensor, and a touch panel.
  • a conductive film having conductive thin wires formed on a substrate includes transparent electrodes for various electronic devices such as solar cells, inorganic EL (Electro Luminescence) elements, and organic EL elements, electromagnetic wave shields for various display devices, touch panels, and transparent surface shapes. Widely used for heating elements. In particular, in recent years, the rate of mounting touch panels on mobile phones, portable game devices, and the like has increased, and the demand for conductive films for capacitive touch panel sensors that can detect multiple points is rapidly expanding. .
  • a substrate, a detection electrode used for detecting an input position provided on the surface of the substrate, and a lead wiring for applying a voltage to the detection electrode ( (Peripheral wiring) is provided.
  • the conductive film is preferably manufactured by a low-temperature process in terms of reducing productivity and damage to each member.
  • the lead-out wiring is made of conductive ink containing silver (silver In many cases, it is formed by ink.
  • the present invention provides a conductive film for a touch panel sensor that has a lead wire that has excellent adhesion and that can be miniaturized, and that has high electrical connectivity between the lead wire and the detection electrode. Let it be an issue. Moreover, this invention also makes it a subject to provide the touchscreen sensor containing the said conductive film for touchscreen sensors, and a touchscreen.
  • the present inventors placed a plating layer containing a predetermined functional group on a substrate and applied a plating catalyst or a precursor thereof to the plating layer. It has been found that the above-mentioned problems can be solved by forming a lead-out wiring by plating and providing a connection portion for electrically connecting the detection electrode and the lead-out wiring. That is, the present inventors have found that the above problem can be solved by the following configuration.
  • a conductive film for a touch panel sensor which is a connected wiring.
  • a pattern-like to-be-plated layer gives energy to a to-be-plated layer forming composition containing the compound which has a functional group and polymeric group which interact with a plating catalyst or its precursor, in pattern shape
  • the conductive film for a touch panel sensor according to (1) which is a layer to be formed.
  • the lead-out wiring gives a plating catalyst or a precursor thereof to the layer to be plated, performs a plating process on the layer to be plated to which the plating catalyst or the precursor is applied, forms a metal layer, and patterns the metal layer A conductive film for a touch panel sensor, which is a wiring formed by etching into a shape.
  • the detection electrode is an electrode formed by a sputtering method or a vapor deposition method.
  • a touch panel sensor comprising the conductive film for a touch panel sensor according to any one of (1) to (7).
  • a touch panel comprising the conductive film for a touch panel sensor according to any one of (1) to (7).
  • the conductive film for touchscreen sensors which has the lead wiring which is excellent in adhesiveness and which can be refined
  • the touch panel sensor containing the said conductive film for touch panel sensors, and a touch panel can also be provided.
  • FIG. 2 is a cross-sectional view taken along a cutting line AA shown in FIG.
  • FIG. 2 is a cross-sectional view taken along a cutting line BB shown in FIG.
  • FIG. 6 is a cross-sectional view taken along a cutting line CC shown in FIG. It is sectional drawing which shows other embodiment of the manufacturing method of extraction wiring in order of a process.
  • FIG. 9 is a cross-sectional view taken along a cutting line DD shown in FIG. It is a top view of 4th Embodiment of the electroconductive film for touchscreen sensors of this invention.
  • FIG. 11 is a cross-sectional view taken along a cutting line EE shown in FIG.
  • a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
  • drawings in the present invention are schematic diagrams, and the thickness relationships and positional relationships of the layers do not necessarily match the actual ones.
  • One of the features of the conductive film for a touch panel sensor of the present invention is that a plating catalyst or a precursor thereof is applied to a layer to be plated having a predetermined functional group, and then a plating process is performed to form a lead wiring.
  • a conductive connection portion that electrically joins the detection electrode and the lead-out wiring is provided.
  • the lead-out wiring can be manufactured on the pattern-like plated layer. In other words, by reducing the line width of the layer to be plated that is the base layer of the lead wiring, the line width of the lead wiring to be formed can be made fine.
  • the wiring of the lead wiring can be controlled by controlling the etching range. The width can be reduced. Further, since the layer to be plated is disposed between the substrate and the lead wiring, the adhesion of the lead wiring is also excellent. In addition, when producing extraction wiring using the said to-be-plated layer, the present inventors discovered that joining property with a detection electrode is not necessarily high.
  • the lead-out wiring is arranged on the layer to be plated, if the lead-out wiring is formed on the detection electrode via the layer to be plated, the conductivity is insufficient due to the presence of the layer to be plated. Can be considered.
  • the detection electrode is formed on the lead-out wiring, it is considered that the height difference between the lead-out wiring and the detection electrode is likely to occur due to the thickness of the plated layer, and the bonding property between the two is likely to be lowered.
  • the lead-out wiring is formed by a plating process, impurities that are likely to be generated during the plating process appear on the surface of the lead-out wiring, which may cause a decrease in bondability with the detection electrode. Therefore, the present inventors have found that the above problem can be solved by providing a conductive connection portion that electrically connects the detection electrode and the lead-out wiring.
  • FIG. 1 the top view of 1st Embodiment of the electroconductive film for touchscreen sensors of this invention is shown.
  • FIG. 2 is a cross-sectional view taken along the cutting line AA.
  • FIG. 3 is a cross-sectional view taken along the cutting line BB.
  • the conductive film 10 for a touch panel sensor according to the present embodiment includes a central area E I that constitutes an input area that can be input by a user when used as a touch panel sensor, and a central area E. And an outer region E O located outside I.
  • the central region is, in other words, a region where the detection electrode is disposed
  • the outer region EO is, in other words, a peripheral region (peripheral region) where the lead-out wiring is disposed outside the central region.
  • the conductive film 10 for a touch panel sensor includes a substrate 12, a detection electrode 14 disposed on one main surface (on the surface) of the substrate 12, a patterned plated layer 16, a lead-out wiring 18, and conductivity. And a connection unit 24.
  • the detection electrode 14 and the lead wiring 18 are electrically connected via the conductive connection portion 24.
  • the lead-out wiring 18 is disposed on the patterned plated layer 16 disposed on the surface of the substrate 12.
  • the patterned layer 16 is located between the substrate 12 and the lead wiring 18.
  • the said structure is explained in full detail.
  • the patterned plated layer 16, the lead-out wiring 18, and the conductive connection portion 24, which are the features of the present invention, will be described in detail.
  • the patterned plated layer 16 is disposed around the detection electrode 14 (outer region E O ) and has a functional group that interacts with the plating catalyst or its precursor (hereinafter also simply referred to as “interactive group”). It is a patterned layer (layer to be plated).
  • the pattern-like plated layer 16 adsorbs (attaches) a plating catalyst or a precursor thereof used for producing the lead-out wiring according to the function of the interactive group. That is, the patterned plated layer functions as a good receiving layer for the plating catalyst or its precursor.
  • the patterned plated layer 16 is located between the substrate 12 and the lead wiring 18.
  • the patterned plated layer 16 is disposed at a position where the lead wiring 18 is disposed.
  • the arrangement position of the patterned plated layer 16 is not limited to the mode of FIG. 1, and at least a part of the outer region E O on the substrate 12 (at least around the detection electrode 14 on the substrate 12). It is preferable to be disposed on a part of the outer region E 2 O.
  • the thickness of the patterned plated layer 16 is not particularly limited, but is preferably 0.01 to 10 ⁇ m, more preferably 0.2 to 5 ⁇ m, and still more preferably 0.25 to 1.0 ⁇ m from the viewpoint of productivity.
  • the line width of the patterned plated layer 16 is not particularly limited, but is preferably 30 ⁇ m or less, more preferably 15 ⁇ m or less, and more preferably 10 ⁇ m or less from the viewpoint of low resistance of the lead-out wiring arranged on the patterned plated layer. Is more preferable, 0.5 ⁇ m or more is preferable, and 1.0 ⁇ m or more is more preferable.
  • the type of the interactive group contained in the patterned plated layer 16 will be described in detail later.
  • resin for example, (meth) acrylic resin (a bridge
  • Thermosetting Examples thereof include an insulating resin such as a resin or a thermoplastic resin. These materials only need to contain an interactive group.
  • the (meth) acrylic resin is a concept including an acrylic resin and a methacrylic resin.
  • thermosetting resin examples include epoxy resins, phenol resins, polyimide resins, polyester resins, bismaleimide resins, polyolefin resins, isocyanate resins, and crosslinked (meth) acrylic resins.
  • thermoplastic resin examples include phenoxy resin, polyether sulfone, polysulfone, polyphenylene sulfone, polyphenylene sulfide, polyphenyl ether, polyether imide, and non-crosslinked (meth) acrylic resin.
  • the method of forming the patterned plated layer 16 is not particularly limited as long as a patterned layer having a predetermined interactive group is formed, but an embodiment using a composition for forming a plated layer to be described later is preferable. It is done.
  • the lead wiring 18 is a member that plays a role in applying a voltage to the detection electrode 14.
  • the lead-out wiring 18 is disposed in the outer region EO on the substrate 12, one end thereof is electrically connected to the corresponding detection electrode 14 through the conductive connection portion 24, and the other end is disposed with a flexible printed wiring board or the like. Is located in a place. In FIG. 1, five lead wires 18 are shown, but the number is not particularly limited, and a plurality of lead wires 18 are usually arranged according to the number of detection electrodes 14.
  • the thickness of the lead-out wiring 18 is not particularly limited, and an optimum thickness is appropriately selected according to the purpose of use, but is preferably 0.1 ⁇ m or more and preferably 0.5 ⁇ m or more from the viewpoint of conductive characteristics. 1 to 30 ⁇ m is more preferable.
  • the line width of the lead wiring 18 is not particularly limited, but is preferably 30 ⁇ m or less, more preferably 15 ⁇ m or less, further preferably 10 ⁇ m or less, more preferably 0.5 ⁇ m or more, and 1.0 ⁇ m or more from the viewpoint of low resistance of the lead wiring Is more preferable.
  • the type of metal constituting the lead wiring 18 is not particularly limited, and examples thereof include copper, chromium, lead, nickel, gold, silver, tin, and zinc. From the viewpoint of conductivity, copper, gold, silver Are preferable, and copper and silver are more preferable.
  • the manufacturing method of the patterned plated layer 16 and the lead wiring 18 is not particularly limited, but the step of forming the patterned plated layer on the substrate is easy in that the formed lead wiring 18 is easily miniaturized (step 1). It is preferable to carry out the step (step 2) of forming the lead wiring on the patterned layer to be plated.
  • steps 1-4 members and materials used in each process and the procedure thereof will be described in detail.
  • Step 1 Patterned plating layer forming step
  • energy is applied in a pattern to a composition for forming a plating layer containing a compound having a functional group and a polymerizable group that interacts with the plating catalyst or its precursor, and the patterned plating layer is formed into a substrate. It is a process of forming on top. More specifically, first, as shown in FIG. 4 (A), a coating film 20 of the composition for forming a layer to be plated was formed on the substrate 12, and obtained as shown in FIG. 4 (B). By applying energy to the coating film 20 as indicated by the black arrows, the reaction of the polymerizable group is promoted to cure, and then the region to which no energy has been applied is removed to remove the pattern covering.
  • the patterned plated layer 16 formed by the above process adsorbs (attaches) the plating catalyst or its precursor in the process 2 to be described later according to the function of the interactive group.
  • a polymeric group is utilized for the coupling
  • composition for forming a layer to be plated contains a compound having an interactive group and a polymerizable group.
  • the interactive group is intended to mean a functional group capable of interacting with a plating catalyst or a precursor thereof applied to the patterned plating layer in a process described later. For example, an electrostatic interaction with the plating catalyst or a precursor thereof is performed.
  • a functional group that can be formed, or a nitrogen-containing functional group, a sulfur-containing functional group, an oxygen-containing functional group, and the like that can be coordinated with a plating catalyst or a precursor thereof can be used.
  • Nitrogen-containing functional groups such as nitro group, nitroso group, azo group, diazo group, azide group, cyano group, cyanate group (R—O—CN); ether group, hydroxyl group, phenolic hydroxyl group, carboxyl group, Carbonate group, carbonyl group, ester group, group containing N-oxide structure, S Oxygen
  • a salt thereof can also be used.
  • an ionic polar group such as a carboxyl group, a sulfonic acid group, a phosphoric acid group, and a boronic acid group, an ether group, or A cyano group is preferable, and a carboxyl group or a cyano group is more preferable.
  • Two or more types of interactive groups may be contained in the compound. The number of interactive groups contained in the compound is not particularly limited, and may be one or two or more.
  • the polymerizable group is a functional group that can form a chemical bond by applying energy, and examples thereof include a radical polymerizable group and a cationic polymerizable group.
  • a radical polymerizable group is preferable from the viewpoint of more excellent reactivity.
  • radical polymerizable groups include acrylic acid ester groups (acryloyloxy groups), methacrylic acid ester groups (methacryloyloxy groups), itaconic acid ester groups, crotonic acid ester groups, isocrotonic acid ester groups, maleic acid ester groups, and the like.
  • Examples include unsaturated carboxylic acid ester groups, styryl groups, vinyl groups, acrylamide groups, and methacrylamide groups.
  • a methacryloyloxy group, an acryloyloxy group, a vinyl group, a styryl group, an acrylamide group, and a methacrylamide group are preferable, and a methacryloyloxy group, an acryloyloxy group, and a styryl group are particularly preferable.
  • Two or more polymerizable groups may be contained in the compound.
  • the number of polymerizable groups contained in the compound is not particularly limited, and may be one or two or more.
  • the compound may be a low molecular compound or a high molecular compound.
  • a low molecular weight compound intends a compound having a molecular weight of less than 1000, and a high molecular weight compound intends a compound having a molecular weight of 1000 or more.
  • the low molecular compound having a polymerizable group corresponds to a so-called monomer.
  • the polymer compound may be a polymer having a predetermined repeating unit. Moreover, as a compound, only 1 type may be used and 2 or more types may be used together.
  • the weight average molecular weight of the polymer is not particularly limited, but is preferably 1000 or more and 700,000 or less, and more preferably 2000 or more and 200,000 or less, from the viewpoint of better handleability such as solubility. In particular, from the viewpoint of polymerization sensitivity, it is preferably 20000 or more.
  • the method for synthesizing such a polymer having a polymerizable group and an interactive group is not particularly limited, and a known synthesis method (see paragraphs [0097] to [0125] of Patent Publication 2009-280905) is used.
  • a repeating unit having a polymerizable group represented by the following formula (a) (hereinafter also referred to as a polymerizable group unit as appropriate) and an interaction represented by the following formula (b)
  • a copolymer containing a repeating unit having a functional group (hereinafter also referred to as an interactive group unit as appropriate).
  • R 1 to R 5 are each independently a hydrogen atom or a substituted or unsubstituted alkyl group (for example, a methyl group, an ethyl group, a propyl group, a butyl group) Etc.).
  • the kind of the substituent is not particularly limited, and examples thereof include a methoxy group, a chlorine atom, a bromine atom, or a fluorine atom.
  • R 1 is preferably a hydrogen atom, a methyl group, or a methyl group substituted with a bromine atom.
  • R 2 is preferably a hydrogen atom, a methyl group, or a methyl group substituted with a bromine atom.
  • R 3 is preferably a hydrogen atom.
  • R 4 is preferably a hydrogen atom.
  • R 5 is preferably a hydrogen atom, a methyl group, or a methyl group substituted with a bromine atom.
  • X, 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 divalent aliphatic hydrocarbon group (preferably having 1 to 8 carbon atoms, for example, an alkylene group such as a methylene group, an ethylene group, and a propylene group), a substituted or unsubstituted group.
  • a divalent aromatic hydrocarbon group (preferably having 6 to 12 carbon atoms, such as a phenylene group), —O—, —S—, —SO 2 —, —N (R) — (R: alkyl group), And —CO—, —NH—, —COO—, —CONH—, or a combination thereof (for example, an alkyleneoxy group, an alkyleneoxycarbonyl group, an alkylenecarbonyloxy group, and the like).
  • a single bond, ester group (—COO—), amide group (—CONH—), ether group (— O—) or a substituted or unsubstituted divalent aromatic hydrocarbon group is preferable, and a single bond, an ester group (—COO—), or an amide group (—CONH—) is more preferable.
  • L 1 and L 2 each independently represent a single bond or a substituted or unsubstituted divalent organic group.
  • a divalent organic group it is synonymous with the divalent organic group described by X, Y, and Z mentioned above.
  • L 1 is an aliphatic hydrocarbon group or a divalent organic group having a urethane bond or a urea bond (for example, an aliphatic hydrocarbon) in that the polymer is easily synthesized and the adhesion of the lead wiring is more excellent. Group), and those having a total carbon number of 1 to 9 are preferred.
  • the total number of carbon atoms of L 1 means the total number of carbon atoms contained in the divalent organic group or a substituted or unsubstituted represented by L 1.
  • L 2 may be a single bond, a divalent aliphatic hydrocarbon group, a divalent aromatic hydrocarbon group, or a combination of these in terms of better adhesion of the lead-out wiring.
  • L 2 preferably has a single bond or a total carbon number of 1 to 15, and is particularly preferably unsubstituted.
  • the total number of carbon atoms of L 2 means the total number of carbon atoms contained in the divalent organic group or a substituted or unsubstituted represented by L 2.
  • W represents an interactive group.
  • the definition of the interactive group is as described above.
  • the content of the polymerizable group unit is preferably 5 to 50 mol% with respect to all repeating units in the polymer from the viewpoint of reactivity (curability, polymerization) and suppression of gelation during synthesis, 5 to 40 mol% is more preferable.
  • the content of the interactive group unit is preferably 5 to 95 mol%, preferably 10 to 95 mol%, based on all repeating units in the polymer, from the viewpoint of adsorptivity to the plating catalyst or its precursor. More preferred.
  • the repeating unit represented by the formula (A) is the same as the repeating unit represented by the above formula (a), and the description of each group is also the same.
  • R 5, X and L 2 in the repeating unit represented by formula (B) is the same as R 5, X and L 2 in the repeating unit represented by formula (b), a description of each group Is the same.
  • Wa in the formula (B) represents a group that interacts with the plating catalyst or its precursor, excluding the hydrophilic group represented by V described later or its precursor group. Of these, a cyano group and an ether group are preferable.
  • each R 6 independently represents a hydrogen atom or a substituted or unsubstituted alkyl group.
  • U represents a single bond or a substituted or unsubstituted divalent organic group.
  • the definition of a bivalent organic group is synonymous with the divalent organic group represented by X, Y, and Z mentioned above.
  • U is a single bond, an ester group (—COO—), an amide group (—CONH—), an ether group (—O—), or an ether group in that the synthesis of the polymer is easy and the adhesion of the lead wiring is more excellent.
  • a substituted or unsubstituted divalent aromatic hydrocarbon group is preferred.
  • L 3 represents a single bond or a substituted or unsubstituted divalent organic group.
  • the definition of a divalent organic group is synonymous with the divalent organic group represented by L 1 and L 2 described above.
  • L 3 is a single bond, a divalent aliphatic hydrocarbon group, a divalent aromatic hydrocarbon group, or a combination thereof in that the polymer is easily synthesized and the adhesion of the lead-out wiring is better. It is preferable that
  • V represents a hydrophilic group or a precursor group thereof.
  • the hydrophilic group is not particularly limited as long as it is a hydrophilic group, and examples thereof include a hydroxyl group and a carboxylic acid group.
  • the precursor group of the hydrophilic group means a group that generates a hydrophilic group by a predetermined treatment (for example, treatment with acid or alkali). For example, a carboxyl group protected with THP (2-tetrahydropyranyl group) Group and the like.
  • the hydrophilic group is preferably an ionic polar group in terms of interaction with the plating catalyst or its precursor.
  • the ionic polar group 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 from the viewpoint of moderate acidity (does not decompose other functional groups).
  • the preferred content of each unit in the second preferred embodiment of the polymer is as follows.
  • the content of the repeating unit represented by the formula (A) is 5 to 50 with respect to all the repeating units in the polymer from the viewpoint of reactivity (curability, polymerizability) and suppression of gelation during synthesis.
  • the mol% is preferable, and 5 to 30 mol% is more preferable.
  • the content of the repeating unit represented by the formula (B) is preferably 5 to 75 mol% with respect to all the repeating units in the polymer, from the viewpoint of adsorptivity to the plating catalyst or its precursor, and 10 to 70 mol. % Is more preferable.
  • the content of the repeating unit represented by the formula (C) is preferably from 10 to 70 mol%, preferably from 20 to 60 mol%, based on all repeating units in the polymer, from the viewpoints of developability with an aqueous solution and moisture-resistant adhesion. Is more preferable, and 30 to 50 mol% is more preferable.
  • the polymer can be prepared by known methods (eg, the methods in the literature listed above).
  • R 11 to R 13 each independently represents a hydrogen atom or a substituted or unsubstituted alkyl group.
  • the unsubstituted alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group.
  • the substituted alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group substituted with a methoxy group, a chlorine atom, a bromine atom, or a fluorine atom.
  • R 11 is preferably a hydrogen atom or a methyl group.
  • R 12 is preferably a hydrogen atom.
  • R 13 is preferably a hydrogen atom.
  • L 10 represents a single bond or a divalent organic group.
  • the divalent organic group include a substituted or unsubstituted aliphatic hydrocarbon group (preferably having 1 to 8 carbon atoms), a substituted or unsubstituted aromatic hydrocarbon group (preferably having 6 to 12 carbon atoms), —O —, —S—, —SO 2 —, —N (R) — (R: alkyl group), —CO—, —NH—, —COO—, —CONH—, or a combination thereof (for example, alkylene Oxy group, alkyleneoxycarbonyl group, alkylenecarbonyloxy group, etc.).
  • a substituted or unsubstituted aliphatic hydrocarbon group a methylene group, an ethylene group, a propylene group, or a butylene group, or these groups are substituted with a methoxy group, a chlorine atom, a bromine atom, a fluorine atom, or the like Those are preferred.
  • the substituted or unsubstituted aromatic hydrocarbon group an unsubstituted phenylene group or a phenylene group substituted with a methoxy group, a chlorine atom, a bromine atom, a fluorine atom or the like is preferable.
  • one preferred embodiment of L 10 includes —NH—aliphatic hydrocarbon group— or —CO—aliphatic hydrocarbon group—.
  • W is synonymous with the definition of W in Formula (b), and represents an interactive group.
  • the definition of the interactive group is as described above.
  • Formula (X) as a suitable aspect of W, an ionic polar group is mentioned, A carboxylic acid group is more preferable.
  • R 10 represents a hydrogen atom, a metal cation, or a quaternary ammonium cation.
  • metal cations include alkali metal cations (sodium ions, calcium ions), copper ions, palladium ions, silver ions, and the like.
  • a metal cation a monovalent or bivalent thing is mainly used, and when bivalent thing (for example, palladium ion) is used, n mentioned later represents 2.
  • the quaternary ammonium cation include tetramethylammonium ion and tetrabutylammonium ion.
  • L 10 in the formula (1) are the same as defined in L 10 in the above-mentioned formula (X), a single bond, or a divalent organic group.
  • the definition of the divalent organic group is as described above.
  • R 11 ⁇ R 13 in the formula (1) has the same meaning as the definition of R 11 ⁇ R 13 in the above-mentioned formula (X), represents a hydrogen atom or a substituted or unsubstituted alkyl group,.
  • the preferred embodiments of R 11 to R 13 are as described above.
  • n represents an integer of 1 or 2. Especially, it is preferable that n is 1 from a viewpoint of the availability of a compound.
  • a compound represented by the formula (2) may be mentioned.
  • L 11 represents an ester group (—COO—), an amide group (—CONH—), or a phenylene group.
  • L 12 represents a single bond, a divalent aliphatic hydrocarbon group (preferably having 1 to 8 carbon atoms, more preferably 3 to 5 carbon atoms), or a divalent aromatic hydrocarbon group.
  • the aliphatic hydrocarbon group may be linear, branched or cyclic.
  • the molecular weight of the compound represented by the formula (1) is not particularly limited, but is preferably from 100 to 1,000, more preferably from 100 to 300, from the viewpoints of volatility, solubility in a solvent, film formability, and handleability. preferable.
  • the content of the above compound in the composition for forming a plated layer is not particularly limited, but is preferably 2 to 50% by mass, more preferably 5 to 30% by mass with respect to the total amount of the composition. If it is in the said range, the handleability of a composition is excellent and it is easy to control the layer thickness of a pattern-like to-be-plated layer.
  • the composition for forming a layer to be plated preferably contains a solvent from the viewpoint of handleability.
  • Solvents that can be used are not particularly limited. For example, water; alcohol solvents such as methanol, ethanol, propanol, ethylene glycol, 1-methoxy-2-propanol, glycerin, propylene glycol monomethyl ether; acids such as acetic acid; acetone, methyl ethyl ketone Ketone solvents such as cyclohexanone; amide solvents such as formamide, dimethylacetamide and N-methylpyrrolidone; nitrile solvents such as acetonitrile and propionitrile; ester solvents such as methyl acetate and ethyl acetate; dimethyl carbonate and diethyl carbonate Other examples include carbonate solvents such as ether solvents, glycol solvents, amine solvents, thiol solvents, and halogen solvents.
  • the content of the solvent in the composition for forming a layer to be plated is not particularly limited, but is preferably 50 to 98% by mass, more preferably 70 to 95% by mass with respect to the total amount of the composition. If it is in the said range, the handleability of a composition is excellent and it is easy to control the layer thickness of a pattern-like to-be-plated layer.
  • a polymerization initiator may be contained in the composition for forming a layer to be plated. By including the polymerization initiator, bonds between the compounds and between the compound and the substrate are further formed, and as a result, a lead-out wiring having better adhesion can be obtained.
  • a polymerization initiator used For example, a thermal polymerization initiator, a photoinitiator, etc. can be used.
  • photopolymerization initiators include benzophenones, acetophenones, ⁇ -aminoalkylphenones, benzoins, ketones, thioxanthones, benzyls, benzyl ketals, oxime esters, anthrones, tetramethylthiuram mono Mention may be made of sulfides, bisacylphosphine oxides, acylphosphine oxides, anthraquinones, azo compounds and the like and their derivatives.
  • thermal polymerization initiator include a diazo compound or a peroxide compound.
  • the content of the polymerization initiator is preferably 0.01 to 1% by mass with respect to the total amount of the composition, and preferably 0.1 to 0.001. More preferably, it is 5 mass%. If it is in the said range, it is excellent in the handleability of a composition and the adhesiveness of the extraction wiring obtained is more excellent.
  • the composition for forming a layer to be plated may contain a monomer (excluding the compound represented by the above formula (X) or formula (1)). By including the monomer, the crosslink density in the patterned layer to be plated can be appropriately controlled.
  • the monomer to be used is not particularly limited, and examples thereof include compounds having an ethylenically unsaturated bond as compounds having addition polymerizability, and compounds having an epoxy group as compounds having ring-opening polymerizability.
  • a polyfunctional monomer means a monomer having two or more polymerizable groups.
  • a monomer having 2 to 6 polymerizable groups it is preferable to use a monomer having 2 to 6 polymerizable groups.
  • the molecular weight of the polyfunctional monomer used is preferably 150 to 1000, more preferably 200 to 700, from the viewpoint of molecular mobility during the crosslinking reaction that affects the reactivity.
  • the interval (distance) between a plurality of polymerizable groups is preferably 1 to 15 atoms, and more preferably 6 or more and 10 or less.
  • composition for forming a layer to be plated other additives (for example, sensitizer, curing agent, polymerization inhibitor, antioxidant, antistatic agent, ultraviolet absorber, filler, particle, flame retardant, surfactant) , Lubricants, plasticizers, etc.) may be added as necessary.
  • additives for example, sensitizer, curing agent, polymerization inhibitor, antioxidant, antistatic agent, ultraviolet absorber, filler, particle, flame retardant, surfactant
  • Lubricants plasticizers, etc.
  • composition for forming a plating layer containing a compound having an interactive group and a polymerizable group has been described.
  • a composition for forming a layer to be plated containing a compound having a polymerizable group may also be used.
  • the definitions of the interactive group and the polymerizable group are as described above.
  • the compound having an interactive group is a compound having an interactive group.
  • the definition of the interactive group is as described above.
  • Such a compound may be a low molecular compound or a high molecular compound.
  • the polymer for example, polyacrylic acid
  • the polymer which has a repeating unit represented by the formula (b) mentioned above is mentioned.
  • the compound having an interactive group does not contain a polymerizable group.
  • the compound having a polymerizable group is a so-called monomer, and is preferably a polyfunctional monomer having two or more polymerizable groups in that the formed layer to be plated is more excellent in hardness. Specifically, it is preferable to use a monomer having 2 to 6 polymerizable groups as the polyfunctional monomer.
  • the molecular weight of the polyfunctional monomer used is preferably 150 to 1000, more preferably 200 to 700, from the viewpoint of molecular mobility during the crosslinking reaction that affects the reactivity.
  • the distance (distance) between a plurality of polymerizable groups is preferably 1 to 15 and more preferably 6 to 10 in terms of the number of atoms.
  • step 1 the composition for forming a layer to be plated is first disposed on the substrate, but the method is not particularly limited.
  • the composition for forming a layer to be plated is brought into contact with the substrate to form a layer to be plated.
  • the method of forming the coating film (to-be-plated layer precursor layer) of the composition for formation is mentioned. Examples of this method include a method (coating method) in which the composition for forming a layer to be plated is applied onto a substrate.
  • the method for coating the composition for forming a layer to be plated on the substrate is not particularly limited, and a known method (for example, spin coating, die coating, dip coating, etc.) can be used.
  • a composition for forming a layer to be plated is applied on a substrate and, if necessary, a drying treatment is performed to remove the remaining solvent to form a coating film.
  • the conditions for the drying treatment are not particularly limited, but are preferably carried out at room temperature to 220 ° C. (preferably 50 to 120 ° C.) for 1 to 30 minutes (preferably 1 to 10 minutes) from the viewpoint of better productivity. .
  • the method for applying energy in a pattern to the coating film containing the compound on the substrate is not particularly limited.
  • a heat treatment or an exposure process (light irradiation process)
  • the exposure process is preferable because the process is completed in a short time.
  • the polymerizable group in the compound is activated, crosslinking between the compounds occurs, and the curing of the layer proceeds.
  • UV (ultraviolet light) lamp, light irradiation with visible light, or the like is used.
  • the light source include a mercury lamp, a metal halide lamp, a xenon lamp, a chemical lamp, and a carbon arc lamp.
  • Examples of radiation include electron beams, X-rays, ion beams, and far infrared rays.
  • Specific examples of preferred embodiments include scanning exposure with an infrared laser, high-illuminance flash exposure such as a xenon discharge lamp, and infrared lamp exposure.
  • the exposure time varies depending on the reactivity of the compound and the light source, but is usually between 10 seconds and 5 hours.
  • the exposure energy may be about 10 to 8000 mJ, preferably 50 to 3000 mJ.
  • the method in particular which implements the said exposure process in a pattern form is not restrict
  • an air dryer an oven, an infrared dryer, a heating drum, or the like can be used.
  • the removal method is not particularly limited, and an optimal method is appropriately selected depending on the compound used.
  • a method using an alkaline solution preferably pH: 13.0 to 13.8 as a developing solution can be mentioned.
  • an alkaline solution preferably pH: 13.0 to 13.8
  • the soaking method is preferred.
  • the dipping time is preferably about 1 to 30 minutes from the viewpoint of productivity and workability.
  • a method in which a solvent in which the above compound is dissolved is used as a developing solution and immersed in the developing solution.
  • Step 2 applies a plating catalyst or a precursor thereof to the patterned plating layer formed in Step 1 above, and performs a plating process on the patterned plating layer provided with the plating catalyst or the precursor thereof. This is a step of forming a lead-out wiring on the patterned layer to be plated. As shown in FIG. 4D, by carrying out this step, the lead-out wiring 18 is arranged on the patterned layer 16 to be plated.
  • step 2-1 a step of applying a plating catalyst or a precursor thereof to the patterned layer to be plated (step 2-1), and a step of performing a plating process on the patterned layer of plating to which the plating catalyst or its precursor has been applied This will be described separately in (Step 2-2).
  • Step 2-1 Plating catalyst application step
  • a plating catalyst or a precursor thereof is applied to the patterned layer to be plated.
  • the interactive group derived from the compound adheres (adsorbs) the applied plating catalyst or its precursor depending on its function.
  • a plating catalyst or a precursor thereof is applied in the layer to be plated and on the surface of the layer to be plated.
  • the plating catalyst or a precursor thereof functions as a catalyst or an electrode for plating treatment. Therefore, the type of plating catalyst or precursor used is appropriately determined depending on the type of plating treatment.
  • the plating catalyst used or its precursor is an electroless plating catalyst or its precursor.
  • the electroless plating catalyst or its precursor will be described in detail.
  • any catalyst can be used as long as it becomes an active nucleus at the time of electroless plating.
  • a metal (Ni) having catalytic ability for autocatalytic reduction reaction and those known as metals capable of electroless plating with a lower ionization tendency).
  • Specific examples include Pd, Ag, Cu, Ni, Pt, Au, and Co. Of these, Ag, Pd, Pt, and Cu are particularly preferable because of their high catalytic ability.
  • a metal colloid may be used as the electroless plating catalyst.
  • the electroless plating catalyst precursor used in this step can be used without particular limitation as long as it can become an electroless plating catalyst by a chemical reaction.
  • the metal ions of the metals mentioned as the electroless plating catalyst are mainly used.
  • the metal ion that is an electroless plating catalyst precursor becomes a zero-valent metal that is an electroless plating catalyst by a reduction reaction.
  • the metal ion that is the electroless plating catalyst precursor may be changed to a zero-valent metal by a reduction reaction separately to be used as an electroless plating catalyst.
  • the electroless plating catalyst precursor may be immersed in an electroless plating bath and changed to a metal (electroless plating catalyst) by a reducing agent in the electroless plating bath.
  • the metal ion which is an electroless plating catalyst precursor is provided to the patterned layer 16 by using a metal salt.
  • the metal salt used is not particularly limited as long as it is dissolved in a suitable solvent and dissociated into a metal ion and a base (anion), and M (NO 3 ) n , MCl n , M 2 / n (SO 4 ), M 3 / n (PO 4 ) (M represents an n-valent metal atom), and the like.
  • a metal ion the thing which said metal salt dissociated can be used suitably. For example, Ag ion, Cu ion, Ni ion, Co ion, Pt ion, Pd ion can be mentioned.
  • a zero-valent metal can also be used as a catalyst used for direct electroplating without electroless plating.
  • a solution (plating catalyst solution) in which the plating catalyst or the precursor thereof is dispersed or dissolved in an appropriate solvent is prepared, and the solution May be applied on the patterned layer to be plated, or a substrate on which the patterned layer to be plated is immersed in the solution.
  • solvent water and an organic solvent are used suitably.
  • the organic solvent is preferably a solvent that can penetrate the patterned layer to be plated, for example, acetone, methyl acetoacetate, ethyl acetoacetate, ethylene glycol diacetate, cyclohexanone, acetylacetone, acetophenone, 2- (1-cyclohexenyl) cyclohexanone.
  • acetone methyl acetoacetate, ethyl acetoacetate, ethylene glycol diacetate, cyclohexanone, acetylacetone, acetophenone, 2- (1-cyclohexenyl) cyclohexanone.
  • Propylene glycol diacetate, triacetin, diethylene glycol diacetate, dioxane, N-methylpyrrolidone, dimethyl carbonate, dimethyl cellosolve and the like can be used.
  • the pH of the catalyst-providing liquid containing the plating catalyst or its precursor and the solvent is not particularly limited. It is preferably 0 to 7.0, more preferably 3.2 to 6.8, and even more preferably 3.5 to 6.6.
  • the method for preparing the catalyst-imparting solution is not particularly limited, and a predetermined metal salt is dissolved in an appropriate solvent, and the pH is adjusted to a predetermined range using an acid or an alkali as necessary.
  • the concentration of the plating catalyst or its precursor in the solution is not particularly limited, but is preferably 0.001 to 50% by mass, and more preferably 0.005 to 30% by mass.
  • the contact time is preferably about 30 seconds to 24 hours, more preferably about 1 minute to 1 hour.
  • the amount of adsorption of the plating catalyst or precursor of the patterned layer 16 varies depending on the type of plating bath used, the type of catalytic metal, the type of interactive base of the patterned layer 16 to be used, the method of use, etc. from the viewpoint of deposition properties, preferably 5 ⁇ 1000mg / m 2, more preferably 10 ⁇ 800mg / m 2, particularly preferably 20 ⁇ 600mg / m 2.
  • a plating treatment is performed on the patterned layer to which the plating catalyst or its precursor is applied.
  • the method for the plating treatment is not particularly limited, and examples thereof include electroless plating treatment or electrolytic plating treatment (electroplating treatment).
  • the electroless plating process may be performed alone, or after the electroless plating process, the electrolytic plating process may be further performed.
  • so-called silver mirror reaction is included as a kind of the electroless plating process. Therefore, for example, the deposited metal ions may be reduced by a silver mirror reaction or the like to form a desired patterned metal layer, and then an electrolytic plating process may be performed.
  • the procedures of the electroless plating process and the electrolytic plating process will be described in detail.
  • the electroless plating treatment refers to an operation of depositing a metal by a chemical reaction using a solution in which metal ions to be deposited as a plating are dissolved.
  • a substrate provided with a pattern-like plated layer provided with an electroless plating catalyst is washed with water to remove excess electroless plating catalyst (metal), and then the electroless plating bath is used. It is preferable to immerse.
  • a known electroless plating bath can be used as the electroless plating bath used.
  • a substrate provided with a patterned plating layer provided with an electroless plating catalyst precursor is immersed in an electroless plating bath in a state where the electroless plating catalyst precursor is adsorbed or impregnated in the patterned plating layer
  • the substrate is washed with water to remove excess electroless plating catalyst precursor (such as a metal salt) and then immersed in an electroless plating bath.
  • electroless plating catalyst precursor such as a metal salt
  • reduction of the electroless plating catalyst precursor and subsequent electroless plating are performed in the electroless plating bath.
  • the electroless plating bath used here a known electroless plating bath can be used as described above.
  • the reduction of the electroless plating catalyst precursor may be performed as a separate process before electroless plating by preparing a catalyst activation liquid (reducing liquid) separately from the embodiment using the electroless plating liquid as described above. Is possible.
  • composition of a general electroless plating bath in addition to a solvent (for example, water), 1. 1. metal ions for plating; 2. reducing agent; Additives (stabilizers) that improve the stability of metal ions are mainly included.
  • the plating bath may contain known additives such as a plating bath stabilizer.
  • the organic solvent used in the electroless plating bath is preferably a solvent that can be used with water, and from this point, ketones such as acetone and alcohols such as methanol, ethanol, and isopropanol are preferably used. Copper, tin, lead, nickel, gold, silver, palladium, and rhodium are known as the types of metals used in the electroless plating bath.
  • the immersion time in the electroless plating bath is preferably about 1 minute to 6 hours, and more preferably about 1 minute to 3 hours.
  • the electroplating layer to which the catalyst or its precursor is applied Plating can be performed.
  • an electroplating process can be performed as needed after the said electroless-plating process.
  • the thickness of the formed lead wiring can be adjusted as appropriate.
  • a method of electroplating a conventionally known method can be used.
  • a metal used for electroplating copper, chromium, lead, nickel, gold
  • the conductive connection portion 24 is a connection portion that electrically connects the detection electrode 14 and the lead wiring 18.
  • the conductive connection portion 24 is disposed so as to be in contact with the detection electrode 14 and the extraction wiring 18.
  • the material constituting the conductive connection portion 24 is not particularly limited as long as it is a material exhibiting conductivity.
  • a metal such as gold (Au), silver (Ag), copper (Cu), aluminum (Al) ( Alloy) and conductive resins.
  • a metal the form of metal fine particles is mentioned.
  • the method for forming the conductive connection portion 24 is not particularly limited, but an embodiment using a conductive composition (so-called conductive paste or conductive ink) is preferable. That is, it is preferable that the electroconductive connection part 24 is a connection part formed from the electroconductive composition.
  • the conductive composition is applied so as to be in contact with the detection electrode 14 and the lead-out wiring 18 by a printing method such as an inkjet method, a screen printing method, a flexographic printing method, or a gravure printing method, and if necessary, It is formed by performing a curing process.
  • the difference between the conductive paste and the conductive ink is a difference in viscosity due to the dispersion medium, and the conductive paste generally has a high viscosity because it contains a polymer component as a dispersion medium.
  • a flexographic printing method can be suitably used.
  • a low molecular component is generally contained as a dispersion medium, so that the viscosity is low, and an ink jet method or the like can be suitably used.
  • the substrate 12 has two main surfaces and is a member that supports the detection electrode 14 in the central region E I and supports the patterned plated layer 16 in the outer region E O.
  • substrate 12 is not restrict
  • an insulating substrate is mentioned, More specifically, a resin substrate, a ceramic substrate, a glass substrate etc. can be used.
  • the resin substrate material include polyethylene terephthalate, polyethylene naphthalate, polyethersulfone, polyacrylic resin, polyurethane resin, polyester, polycarbonate, polysulfone, polyamide, polyarylate, polyolefin, cellulose resin, polyvinyl chloride, Examples thereof include cycloolefin resins.
  • the thickness (mm) of the substrate 12 is not particularly limited, but is preferably 0.05 to 2 mm, more preferably 0.1 to 1 mm, from the viewpoint of the balance between handleability and thinning. Moreover, it is preferable that the board
  • Primer layer adheresion auxiliary layer
  • the adhesion between the substrate and the patterned plating layer (or plating layer) may be affected by the surface state and rigidity of the substrate. Therefore, a primer layer for improving the adhesion between the substrate and the pattern-like plated layer (or the plated layer) may be appropriately disposed on the substrate depending on the type of the substrate. In other words, a primer layer may be interposed between the substrate and the pattern-like plated layer (or plated layer).
  • the surface energy is controlled, the chemical bond with the layer to be plated is formed, or the adhesive force by stress relaxation It is possible to take various measures for improving the adhesion, such as using
  • a low molecular layer or a polymer layer close to the surface energy of the layer to be plated can be used.
  • a low molecular layer or a high molecular layer having a polymerization active site can be used.
  • a rubber-like resin having a low elastic modulus can be used.
  • the thickness of the primer layer is not particularly limited, but is generally preferably 0.01 to 100 ⁇ m, more preferably 0.05 to 20 ⁇ m, and further preferably 0.05 to 10 ⁇ m.
  • the material for the primer layer is not particularly limited, and is preferably a resin having good adhesion to the substrate.
  • Specific examples of the resin may be, for example, a thermosetting resin, a thermoplastic resin, or a mixture thereof.
  • the thermosetting resin an epoxy resin, a phenol resin, a polyimide resin, a polyester resin, a bismaleimide resin, Examples include polyolefin resins and isocyanate resins.
  • thermoplastic resin examples include phenoxy resin, polyether sulfone, polysulfone, polyphenylene sulfone, polyphenylene sulfide, polyphenyl ether, polyether imide, and ABS resin.
  • the thermoplastic resin and the thermosetting resin may be used alone or in combination of two or more.
  • a resin containing a cyano group may be used.
  • an ABS resin or “unit having a cyano group in the side chain” described in JP-A 2010-84196 [0039] to [0063] is included.
  • Polymer may be used.
  • rubber components such as NBR rubber (acrylonitrile / butadiene rubber) and SBR rubber (styrene / butadiene rubber) can be used.
  • One preferred embodiment of the material constituting the primer layer includes a polymer having a conjugated diene compound unit that may be hydrogenated.
  • the conjugated diene compound unit means a repeating unit derived from a conjugated diene compound.
  • the conjugated diene compound is not particularly limited as long as it is a compound having a molecular structure having two carbon-carbon double bonds separated by one single bond.
  • One preferred embodiment of the repeating unit derived from a conjugated diene compound includes a repeating unit produced by a polymerization reaction of a compound having a butadiene skeleton.
  • the conjugated diene compound unit may be hydrogenated.
  • the adhesion of the patterned metal layer is preferably improved. That is, the double bond in the repeating unit derived from the conjugated diene compound may be hydrogenated.
  • the above-mentioned interactive group may be contained in the polymer having a conjugated diene compound unit that may be hydrogenated.
  • this polymer examples include acrylonitrile butadiene rubber (NBR), carboxyl group-containing nitrile rubber (XNBR), acrylonitrile-butadiene-isoprene rubber (NBIR), acrylonitrile-butadiene-styrene copolymer (ABS resin), or These hydrogenated products (for example, hydrogenated acrylonitrile butadiene rubber) and the like can be mentioned.
  • NBR acrylonitrile butadiene rubber
  • XNBR carboxyl group-containing nitrile rubber
  • NBIR acrylonitrile-butadiene-isoprene rubber
  • ABS resin acrylonitrile-butadiene-styrene copolymer
  • the primer layer contains other additives (for example, sensitizers, antioxidants, antistatic agents, ultraviolet absorbers, fillers, particles, flame retardants, surfactants, lubricants, plasticizers, etc.). Also good.
  • additives for example, sensitizers, antioxidants, antistatic agents, ultraviolet absorbers, fillers, particles, flame retardants, surfactants, lubricants, plasticizers, etc.
  • the method for forming the primer layer is not particularly limited, and a method of laminating a resin to be used on a substrate, a method in which a necessary component is dissolved in a soluble solvent, and a method such as coating and drying on a substrate surface Etc.
  • the heating temperature and time in the coating method may be selected so that the coating solvent can be sufficiently dried, but from the viewpoint of production suitability, the heating temperature should be 200 ° C. or less and the heating condition within the range of 60 minutes. It is preferable to select heating conditions in the range of heating temperature 40 to 100 ° C. and time 20 minutes or less.
  • an optimal solvent for example, cyclohexanone or methyl ethyl ketone is appropriately selected according to the resin to be used.
  • the detection electrode 14 is a sensing electrode that senses a change in capacitance in a touch panel sensor including the conductive film for a touch panel sensor of the present embodiment, and constitutes a sensing unit (sensing unit). That is, when the fingertip is brought into contact with the touch panel, the mutual capacitance between the detection electrode 14 and the other electrode changes, and the position of the fingertip is calculated by an IC (integrated circuit) circuit based on the change amount.
  • the detection electrode 14 has a role of detecting an input position in the X direction of an operator's finger approaching the central region E I and has a function of generating a capacitance between the detection electrode 14 and the finger. .
  • the detection electrodes 14 are electrodes that extend in a first direction (X direction) and are arranged at a predetermined interval in a second direction (Y direction) orthogonal to the first direction. In FIG. 1, five detection electrodes 14 are provided, but the number thereof is not particularly limited, and a plurality of detection electrodes 14 may be provided. In FIG. 1, the detection electrode 14 is a solid film, but may include a predetermined pattern such as a mesh shape.
  • the material that constitutes the detection electrode 14 is not particularly limited, and examples thereof include metal oxides such as indium tin oxide (ITO), tin oxide, zinc oxide, cadmium oxide, gallium oxide, and titanium oxide. Alternatively, a metal or an alloy such as gold (Au), silver (Ag), copper (Cu), or aluminum (Al) may be used.
  • the method for forming the detection electrode 14 is not particularly limited, and a known method can be adopted, but it is preferably formed by, for example, a sputtering method or a vapor deposition method.
  • a flexible printed wiring board or the like may be disposed at a location where the other end of the lead-out wiring 18 (an end portion not on the detection electrode 14 side) is located.
  • the flexible printed wiring board is a board in which a plurality of wirings and terminals are provided on a substrate, and is connected to each other end of the lead-out wiring 18, and a capacitive touch panel sensor and an external device (for example, a display device). Play a role in connecting.
  • Method 1 After the detection electrode 14 is arranged on the substrate 12 at a predetermined position, the patterned plating layer 16 is arranged on the substrate 12 at a predetermined position, and the lead wiring is formed on the patterned plating layer 16. 18 is disposed, and then the conductive connection portion 24 is disposed (method 2): after the patterned plated layer 16 is disposed on the substrate 12 at a predetermined position, the lead wiring is disposed on the patterned plated layer 16.
  • the conductive film 10 for a touch panel sensor described above can be suitably used for a touch panel sensor.
  • two conductive films (film A and film B) for a touch panel sensor are prepared, the detection electrode 14 in the film A and the detection electrode 14 in the film B are opposed, and the detection electrode in the film A 14 and the detection electrode 14 in the film B are orthogonally bonded to each other by attaching an adhesive to the film A and the film B, and, if necessary, connecting other members (for example, a flexible printed circuit board), A capacitive touch panel sensor can be obtained.
  • two conductive films (film A and film B) for the touch panel sensor are prepared, and the detection electrode 14 in the film A and the substrate 12 in the film B are opposed to each other, and the detection electrode 14 in the film A is provided.
  • the film A and the film B are bonded with an adhesive so that the detection electrode 14 in the film B and the detection electrode 14 are orthogonal to each other, and another member (for example, a flexible printed wiring board) is connected as necessary.
  • a capacitive touch panel sensor can also be obtained.
  • the touch panel sensor as described above can be suitably applied to a touch panel (in particular, a capacitive touch panel).
  • FIG. 5 the top view of 2nd Embodiment of the conductive film for touchscreen sensors of this invention is shown.
  • FIG. 6 is a cross-sectional view taken along the cutting line CC.
  • the conductive film 100 for a touch panel sensor shown in FIG. 5 includes a substrate 12, a detection electrode 14, a patterned plated layer 160, and a lead wiring 18 disposed on one main surface (surface) of the substrate 12. And a conductive connection portion 24.
  • the patterned plated layer 160 is disposed over the entire outer region E 2 O.
  • the patterned plated layer 160 is disposed on the surface of the substrate 12 other than the central region E I. Since the conductive film 100 for a touch panel sensor shown in FIG.
  • the patterned plated layer 160 has the same configuration as the patterned plated layer 16 described in the first embodiment, and differs only in the arrangement position on the substrate 12.
  • Examples of the method for forming the patterned plated layer 160 include the same procedure as the method for forming the patterned plated layer 16 described in the first embodiment, and the above-described [Step 1: Patterned plated layer formation]. What is necessary is just to make it the area
  • the manufacturing method of the lead wiring 18 is not particularly limited, but the following process 3 (drawing wiring forming process) is preferably exemplified. Hereinafter, the procedure of step 3 will be described in detail.
  • Step 3 applies a plating catalyst or a precursor thereof to the patterned layer to be plated, and performs a plating process on the layer to be plated to which the plating catalyst or the precursor has been applied.
  • This is a step of forming a layer and etching the resulting metal layer into a pattern to form a lead-out wiring. More specifically, first, as shown in FIG. 7A, the substrate 12 on which the patterned plating layer 160 is arranged is prepared, and then, as shown in FIG. A plating catalyst or a precursor thereof is applied to the plating layer 160 and plating is performed to form the metal layer 30 on the patterned layer 160. Next, as shown in FIG. The lead wire 18 is obtained by etching the layer 30 into a pattern.
  • a plating catalyst or a precursor thereof is applied to the patterned layer to be plated 160, and a plating treatment is performed on the patterned layer 160 to which the plating catalyst or its precursor has been applied. Since the procedure of forming the metal layer 30 on the layer 160 is the same as the procedure of the steps 2-1 and 2-2 described in the first embodiment, detailed description thereof is omitted. Hereinafter, the procedure of the process of forming the lead wiring 18 by etching the metal layer 30 in a pattern will be described in detail.
  • any method can be used to form the lead-out wiring 18, and specifically, a generally known subtractive method (a patterned mask is provided on the metal layer, and a non-mask forming region is etched). After the treatment, the mask is removed and a lead wiring is formed), a semi-additive method (a patterned mask is provided on the metal layer, and a plating process is performed so as to form a metal layer in a non-mask formation region) , A method of removing the mask and performing etching to form a lead-out wiring).
  • the subtractive method is to provide a resist layer on the formed metal layer, form the same pattern as the lead wiring formed by pattern exposure and development, and use the resist pattern as a mask to form the metal layer with an etching solution.
  • Any material can be used as the resist, and negative, positive, liquid, and film-like ones can be used.
  • an etching method any method used at the time of manufacturing a printed wiring board can be used, and wet etching, dry etching, and the like can be used, and may be arbitrarily selected. In terms of operation, wet etching is preferable from the viewpoint of simplicity of the apparatus.
  • an etching solution for example, an aqueous solution of cupric chloride, ferric chloride, or the like can be used.
  • the semi-additive method is to provide a resist layer on the formed metal layer, form the same pattern as the non-metal layer pattern portion by pattern exposure and development, and perform electrolytic plating using the resist pattern as a mask,
  • This is a method of forming a lead-out wiring by performing quick etching after removing the resist pattern and removing the metal layer in a pattern.
  • the resist, the etching solution, etc. can use the same material as the subtractive method.
  • the above-described method can be used as a method of electrolytic plating treatment.
  • the metal particles formed by reducing metal ions contained in the pattern plating layer located immediately below the metal layer to be removed are combined as necessary. It may be removed.
  • the removal method in particular of the said metal particle is not restrict
  • FIG. 8 the top view of 3rd Embodiment of the conductive film for touchscreen sensors of this invention is shown.
  • FIG. 9 is a cross-sectional view taken along the cutting line DD.
  • a conductive film 200 for a touch panel sensor shown in FIG. 8 includes a substrate 12, a plated layer 22 disposed on the substrate 12, a detection electrode 14 disposed on the plated layer 22, lead wires 18, And a conductive connection portion 24.
  • the layer to be plated 22 is disposed over the entire surface of the substrate 12, and the detection electrode 14 and the lead wiring 18 are disposed on the layer to be plated 22.
  • the conductive film 200 for a touch panel sensor shown in FIG. 8 is for the touch panel sensor shown in FIG.
  • the plated layer 22 is used instead of the patterned plated layer 16 and the arrangement of each member is changed. Since it has the same configuration as that of the conductive film 10, the same reference numeral is given to the same component, the description thereof is omitted, and the plated layer 22 will be mainly described in detail below.
  • the to-be-plated layer 22 and the pattern-like to-be-plated layer 16 demonstrated in 1st Embodiment differ in the area
  • the to-be-plated layer 22 has an interactive group.
  • the formation method of the to-be-plated layer 22 is not specifically limited, The procedure similar to 1st Embodiment mentioned above is mentioned, The area
  • FIG. 10 shows the top view of 4th Embodiment of the conductive film for touchscreen sensors of this invention.
  • FIG. 11 is a cross-sectional view taken along the cutting line DD. As shown in FIG.
  • the conductive film 300 for a touch panel sensor includes a substrate 12, a detection electrode 14 disposed on both surfaces of the substrate 12, a patterned plated layer 16, lead wires 18, and conductivity. And a connection unit 24. As shown in FIG. 10, the detection electrode 14 disposed on the front surface of the substrate 12 and the detection electrode 14 disposed on the back surface of the substrate 12 are disposed so as to be orthogonal to each other.
  • the ethyl acetate phase was washed four times with 300 mL of distilled water, dried over magnesium sulfate, and 80 g of raw material A was obtained by distilling off ethyl acetate.
  • 47.4 g of raw material A, 22 g of pyridine, and 150 mL of ethyl acetate were placed in a 500 mL three-necked flask and cooled in an ice bath.
  • 25 g of acrylic acid chloride was added dropwise while adjusting the internal temperature to 20 ° C. or lower. Then, it was raised to room temperature and reacted for 3 hours. After completion of the reaction, 300 mL of distilled water was added to stop the reaction.
  • a 500 mL three-necked flask was charged with 8 g of N, N-dimethylacetamide and heated to 65 ° C. under a nitrogen stream.
  • monomer M1 14.3 g, acrylonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) 3.0 g, acrylic acid (manufactured by Tokyo Chemical Industry) 6.5 g, V-65 (manufactured by Wako Pure Chemical Industries) 0.4 g of N
  • a solution of 8 g of N-dimethylacetamide was added dropwise over 4 hours. After completion of the dropwise addition, the reaction solution was further stirred for 3 hours.
  • the obtained polymer 1 was identified using an IR (infrared) measuring machine (manufactured by Horiba, Ltd.). The measurement was performed by dissolving the polymer in acetone and using KBr crystals. As a result of IR measurement, a peak was observed in the vicinity of 2240 cm ⁇ 1 , and it was found that acrylonitrile, which is a nitrile unit, was introduced into the polymer. Moreover, it was found from the acid value measurement that acrylic acid was introduced as a carboxylic acid unit. Further, it was dissolved in heavy DMSO (dimethyl sulfoxide) and measured by Bruker 300 MHz NMR (Nuclear Magnetic Resonance) (AV-300). 4.
  • IR infrared measuring machine
  • a peak corresponding to the nitrile group-containing unit is broadly observed at 2.5-0.7 ppm (5H min), and a peak corresponding to the polymerizable group-containing unit is 7.8-8.1 ppm (1H min). 8-5.6 ppm (1H min), 5.4-5.2 ppm (1H min), 4.2-3.9 ppm (2H min), 3.3-3.5 ppm (2H min), 2.5- A broad peak is observed at 0.7 ppm (6H min), and a peak corresponding to a carboxylic acid-containing unit is broadly observed at 2.5-0.7 ppm (3H min).
  • a polymerizable group-containing unit: a nitrile group-containing unit: It was found that the carboxylic acid group unit 30: 30: 40 (mol%).
  • composition for forming layer to be plated In a 200 ml beaker containing a magnetic stirrer, water (18.95 parts by mass), propylene glycol monomethyl ether (75.8 parts by mass), polymer 1 (5 parts by mass), and IRGACUREOXE02 (manufactured by BASF) (0. 0 parts). 25 parts by mass) was added to prepare a composition for forming a layer to be plated.
  • Example 1 A glass substrate (manufactured by Corning) was heated and dried at 150 ° C. for 1 hour, and then a primer layer forming composition (Nipol 1561 (manufactured by ZEON Corporation) in water dispersion (total solid content concentration: 40.5 parts by mass) ) was spin-coated at 1500 rpm for 1 minute and dried at 120 ° C. for 30 minutes to form a primer layer. Subsequently, the composition for forming a layer to be plated was spin-coated on the primer layer and dried at 80 ° C. for 5 minutes.
  • a primer layer forming composition Nipol 1561 (manufactured by ZEON Corporation) in water dispersion (total solid content concentration: 40.5 parts by mass)
  • total solid content concentration total solid content concentration: 40.5 parts by mass
  • the substrate was irradiated with UV in the atmosphere (energy amount: 2J, 10 mW, wavelength: 256 nm) through a negative mask having a pattern of 3 ⁇ m / 3 ⁇ m line / space, and 1% sodium hydrogen carbonate was used. And developed to form a patterned plated layer (thickness: 0.25 ⁇ m).
  • the glass substrate having the patterned coating layer is coated with Pd catalyst applying liquid MAT-2 (manufactured by Uemura Kogyo).
  • MAT-2A alone (catalyst imparting solution, pH: 3.5) was immersed for 5 minutes at room temperature, and washed twice with pure water. Next, it was immersed in a reducing agent MAB (manufactured by Uemura Kogyo) at 36 ° C. for 5 minutes and washed twice with pure water. Thereafter, it was immersed in an activation treatment solution MEL-3 (manufactured by Uemura Kogyo) at room temperature for 5 minutes, and immersed in electroless plating solution Sulcup PEA (manufactured by Uemura Kogyo) for 60 minutes at room temperature without washing. The masked tape was peeled off and washed twice with pure water to obtain a glass substrate provided with a patterned copper layer (corresponding to a lead-out wiring) on the patterned plated layer.
  • sputtering using an indium oxide-tin oxide target having a composition of indium oxide and tin oxide at a weight ratio of 95: 5 and a packing density of 98% is applied to a region where the patterned copper layer on the glass substrate is not disposed.
  • An ITO layer was formed by the method, and resist patterning and etching were performed by a photolithography method to obtain a patterned ITO layer (corresponding to a detection electrode).
  • conductive ink containing silver nanoparticles NPS-JL manufactured by Harima Chemicals Co., Ltd.
  • Example 2 A glass substrate (manufactured by Corning) was heated and dried at 150 ° C. for 1 hour, and then a primer layer forming composition (Nipol 1561 (manufactured by ZEON Corporation) in water dispersion (total solid content concentration: 40.5 parts by mass) ) was spin-coated at 1500 rpm for 1 minute and dried at 120 ° C. for 30 minutes to form a primer layer. Subsequently, the composition for forming a layer to be plated was spin-coated on the primer layer and dried at 80 ° C. for 5 minutes.
  • a primer layer forming composition Nipol 1561 (manufactured by ZEON Corporation) in water dispersion (total solid content concentration: 40.5 parts by mass)
  • total solid content concentration total solid content concentration: 40.5 parts by mass
  • UV irradiation energy amount: 2 J, 10 mW, wavelength: 256 nm
  • the glass substrate having the layer to be plated is made of MAT-2A made of Pd catalyst application liquid MAT-2 (manufactured by Uemura Kogyo). No. 5 was diluted 5 times at room temperature and washed twice with pure water.
  • a dry resist film (manufactured by Hitachi Chemical; RY3315, film thickness: 15 ⁇ m) was laminated on the obtained copper layer with a vacuum laminator (manufactured by Meiki Seisakusho: MVLP-600) at 70 ° C. and 0.2 MPa.
  • a glass mask capable of forming a comb-type wiring (compliant with JPCA-BU01-2007) as defined in JPCA-ET01 is closely attached to the substrate on which the dry resist film is laminated, and the resist is exposed to light of 70 mJ with an exposure machine having a central wavelength of 405 nm. Irradiated with energy.
  • Development was performed by spraying a 1% Na 2 CO 3 aqueous solution onto the exposed substrate at a spray pressure of 0.2 MPa. Thereafter, the substrate was washed with water and dried to form a resist pattern having a line / space of 8 ⁇ m / 8 ⁇ m.
  • Etching was performed by immersing the substrate on which the resist pattern was formed in an FeCl 3 / HCl aqueous solution (etching solution) at a temperature of 40 ° C. to remove the copper layer present in the region where the resist pattern was not formed.
  • the resist pattern is swollen and peeled off by spraying a 3% NaOH aqueous solution onto the substrate at a spray pressure of 0.2 MPa, neutralized with a 10% sulfuric acid aqueous solution, and washed with water to form a patterned copper layer (drawer).
  • a glass substrate provided with a wiring) was obtained.
  • a patterned ITO layer and a conductive connection part were formed to obtain a conductive film.
  • a patterned silver layer (corresponding to a lead-out wiring) was produced by an inkjet method (DMP2831 made by FUJIFILM Dimatix) using conductive ink (NPS-JL made by Harima Chemicals Co., Ltd.) instead of the patterned copper layer
  • a conductive film was obtained.
  • the ink jet method using conductive ink only a patterned silver layer having a line / space of 100 ⁇ m / 100 ⁇ m was obtained due to a problem in the performance of the apparatus.
  • ⁇ Adhesion evaluation> (Tape peeling test) As an evaluation method, a tape peeling test was performed after the patterned copper layer of Examples 1 and 2 and the patterned silver layer of Comparative Example 1 were formed, and the patterned copper layer or the patterned silver layer was not peeled off. The residual rate remaining above was evaluated according to the following criteria. The tape peeling test was performed according to JIS K5600-5-6. “A”: 90 to 100% remaining “B”: More than 10% peeled
  • ⁇ Connectivity evaluation> (Connection resistance measurement) As an evaluation method, a resistance value between the patterned copper layer (or patterned silver layer) and the patterned ITO layer was measured (manufactured by Hioki Electric Co., Ltd., milliohm high tester 3540), and evaluated according to the following criteria. “A”: When the resistance value is 10 m ⁇ or less “B”: When the resistance value exceeds 10 m ⁇ “C”: When the resistance value cannot be measured and is substantially disconnected
  • Table 1 The evaluation results are summarized in Table 1.
  • “X” in the “Treatment Method” column means a method of forming a patterned copper layer on the patterned layer to be plated, and “Y” indicates that the patterned copper layer is etched by etching the copper layer. Intended for the method of forming.
  • the patterned copper layer (corresponding to the lead-out wiring) in the conductive film for a touch panel sensor of the present invention can be miniaturized and has excellent adhesion. Moreover, the electrical connectivity between the patterned copper layer and the ITO layer (corresponding to the detection electrode) was also high. On the other hand, in Comparative Example 1 using conductive ink, the patterned silver layer (corresponding to the lead-out wiring) could not be refined in the first place, and the adhesiveness of the formed patterned silver layer was inferior.
  • Example 3 A glass substrate (manufactured by Corning) was heated and dried at 150 ° C. for 1 hour, and then a primer layer forming composition (Nipol 1561 (manufactured by ZEON Corporation) in water dispersion (total solid content concentration: 40.5 parts by mass) ) was spin-coated at 1500 rpm for 1 minute and dried at 120 ° C. for 30 minutes to form a primer layer. Subsequently, the composition for forming a layer to be plated was spin-coated on the primer layer at 1500 rpm for 1 minute and dried at 80 ° C. for 5 minutes.
  • a primer layer forming composition Nipol 1561 (manufactured by ZEON Corporation) in water dispersion (total solid content concentration: 40.5 parts by mass)
  • total solid content concentration total solid content concentration: 40.5 parts by mass
  • the substrate is irradiated with UV light (energy amount: 2J, 10 mW, wavelength: 256 nm) in the air through a predetermined negative mask, and developed with 1% sodium hydrogen carbonate, thereby developing the substrate shown in FIG.
  • a patterned plated layer was formed at the same position as the patterned plated layer 16.
  • a patterned copper layer was produced on the patterned plated layer according to the same procedure as in Example 1 using the obtained glass substrate having the patterned plated layer. The obtained patterned copper layer is disposed at the same position as the lead-out wiring 18 in FIG.
  • an ITO layer was produced by sputtering or photolithography so that the ITO layer was disposed at the position of the detection electrode 14 in FIG.
  • a conductive ink containing silver nanoparticles (NPS-JL manufactured by Harima Kasei Co., Ltd.) is used in the inkjet method between the patterned copper layer and the ITO layer so that the conductive connection portion 24 of FIG. 1 is formed. Then, a heat curing treatment was performed to form a conductive connection portion made of silver.
  • the obtained conductive film for a touch panel showed desired effects (miniaturization, low resistance, high adhesion) as in Example 1.
  • the conductive film for touchscreens was obtained according to the procedure similar to the above except having formed the pattern-like to-be-plated layer in the same position as the pattern-like to-be-plated layer 160 of FIG. Furthermore, the conductive film for touch panels of the aspect shown in FIG. 10 was obtained by implementing the said procedure on both surfaces of a glass substrate.

Abstract

The present invention provides: a conductive film that is for a touch panel sensor and has superior adhesiveness, a lead wire that can be more minute, and high electrical connectivity between the lead wire and a detection electrode; a touch panel sensor; and a touch panel. The conductive film for a touch panel sensor is provided with: a substrate; a detection electrode disposed at least at one surface of the substrate; a patterned coated layer disposed at the periphery of the detection electrode on the surface of the substrate at which the detection electrode is disposed, and having a functional group that interacts with a coating catalyst or a precursor thereof; a lead wire disposed on the patterned coated layer; and a conductive connection section that electrically connects the detection electrode and the lead wire. The lead wire is formed by means of a method having at least a step for imparting the coating catalyst or precursor thereof onto the patterned coated layer, and performing coating processing of the patterned coated layer to which the coating catalyst or precursor thereof has been imparted.

Description

タッチパネルセンサー用導電性フィルム、タッチパネルセンサー、タッチパネルConductive film for touch panel sensor, touch panel sensor, touch panel
 本発明は、タッチパネルセンサー用導電性フィルム、タッチパネルセンサー、および、タッチパネルに関する。 The present invention relates to a conductive film for a touch panel sensor, a touch panel sensor, and a touch panel.
 基板上に導電性細線が形成された導電性フィルムは、太陽電池、無機EL(Electro Luminescence)素子、有機EL素子などの各種電子デバイスの透明電極、各種表示装置の電磁波シールド、タッチパネル、透明面状発熱体などに幅広く利用されている。
 特に、近年、携帯電話や携帯ゲーム機器等へのタッチパネルの搭載率が上昇しており、多点検出が可能な静電容量方式のタッチパネルセンサー用の導電性フィルムの需要が急速に拡大している。
 タッチパネルセンサー用の導電性フィルムの一態様として、基板と、基板の表面上に設けられた入力位置を検出するための使用される検出電極と、この検出電極に電圧を印加するための引き出し配線(周辺配線)とが設けられる態様が挙げられる。なお、生産性や各部材へのダメージを減らす点で導電性フィルムは低温プロセスにて製造されることが好ましく、特許文献1などに示されるように、引き出し配線は銀を含む導電性インク(銀インク)などによって形成される場合が多い。
A conductive film having conductive thin wires formed on a substrate includes transparent electrodes for various electronic devices such as solar cells, inorganic EL (Electro Luminescence) elements, and organic EL elements, electromagnetic wave shields for various display devices, touch panels, and transparent surface shapes. Widely used for heating elements.
In particular, in recent years, the rate of mounting touch panels on mobile phones, portable game devices, and the like has increased, and the demand for conductive films for capacitive touch panel sensors that can detect multiple points is rapidly expanding. .
As one aspect of the conductive film for the touch panel sensor, a substrate, a detection electrode used for detecting an input position provided on the surface of the substrate, and a lead wiring for applying a voltage to the detection electrode ( (Peripheral wiring) is provided. Note that the conductive film is preferably manufactured by a low-temperature process in terms of reducing productivity and damage to each member. As shown in Patent Document 1 and the like, the lead-out wiring is made of conductive ink containing silver (silver In many cases, it is formed by ink.
特許4780254号公報Japanese Patent No. 4780254
 一方、タッチパネルの小型の情報端末機器への適用がすすみ、広い入力エリアを確保するため、額縁部分の幅を狭くすること(狭額縁化)が求められている。通常、タッチパネルの額縁部分には引き出し配線があるため、上記要望に対応するためには、引き出し配線の微細化(引き出し配線の幅を狭くすること)が求められる。
 しかしながら、上述したように、特許文献1においては銀インク等が用いられており、このような銀インクのスクリーン印刷技術には配線の微細化や寸法精度の限界がある。
On the other hand, the application of touch panels to small information terminal devices has progressed, and in order to secure a wide input area, it is required to narrow the width of the frame portion (narrow frame). Usually, since there is a lead-out wiring in the frame portion of the touch panel, miniaturization of the lead-out wiring (reducing the width of the lead-out wiring) is required to meet the above demand.
However, as described above, silver ink or the like is used in Patent Document 1, and the screen printing technology of such silver ink has limitations in wiring miniaturization and dimensional accuracy.
 また、引き出し配線の微細化に伴い、耐久性の観点から、引き出し配線の密着性向上も求められている。
 さらには、タッチパネルの接触の検出感度を高める目的のために、検出電極と引き出し配線との高い電気的接続性も求められている。
In addition, with the miniaturization of the lead-out wiring, improvement in the adhesion of the lead-out wiring is also required from the viewpoint of durability.
Furthermore, high electrical connectivity between the detection electrode and the lead-out wiring is also required for the purpose of increasing the touch detection sensitivity.
 本発明は、上記実情に鑑みて、密着性に優れ、微細化が可能な引き出し配線を有し、引き出し配線と検出電極との電気的接続性が高いタッチパネルセンサー用導電性フィルムを提供することを課題とする。
 また、本発明は、上記タッチパネルセンサー用導電性フィルムを含むタッチパネルセンサー、および、タッチパネルを提供することも課題とする。
In view of the above circumstances, the present invention provides a conductive film for a touch panel sensor that has a lead wire that has excellent adhesion and that can be miniaturized, and that has high electrical connectivity between the lead wire and the detection electrode. Let it be an issue.
Moreover, this invention also makes it a subject to provide the touchscreen sensor containing the said conductive film for touchscreen sensors, and a touchscreen.
 本発明者らは、従来技術の問題点について鋭意検討を行ったところ、所定の官能基を含む被めっき層を基板上に配置して、この被めっき層にめっき触媒またはその前駆体を付与してめっき処理を施して引き出し配線を形成すること、および、検出電極と引き出し配線とを電気的に接続する接続部を設けることにより、上記課題を解決できることを見出した。
 つまり、本発明者らは、以下の構成により上記課題が解決できることを見出した。
As a result of diligent investigations on the problems of the prior art, the present inventors placed a plating layer containing a predetermined functional group on a substrate and applied a plating catalyst or a precursor thereof to the plating layer. It has been found that the above-mentioned problems can be solved by forming a lead-out wiring by plating and providing a connection portion for electrically connecting the detection electrode and the lead-out wiring.
That is, the present inventors have found that the above problem can be solved by the following configuration.
(1) 基板と、
 基板の少なくとも一方の表面上に配置された検出電極と、
 基板の検出電極がある側の表面上で、検出電極の周辺に配置され、めっき触媒またはその前駆体と相互作用する官能基を有するパターン状被めっき層と、
 パターン状被めっき層上に配置された引き出し配線と、
 検出電極と引き出し配線とを電気的に接続する導電性接続部とを備え、
 引き出し配線が、パターン状被めっき層にめっき触媒またはその前駆体を付与して、めっき触媒またはその前駆体が付与されたパターン状被めっき層に対してめっき処理を行う工程を少なくとも有する方法により形成された配線である、タッチパネルセンサー用導電性フィルム。
(2) パターン状被めっき層が、めっき触媒またはその前駆体と相互作用する官能基および重合性基を有する化合物を含有する被めっき層形成用組成物に対してパターン状にエネルギーを付与して形成される層である、(1)に記載のタッチパネルセンサー用導電性フィルム。
(3) 基板と、
 基板上に配置された、めっき触媒またはその前駆体と相互作用する官能基を有する被めっき層と、
 被めっき層上に配置された検出電極と、
 被めっき層上で、検出電極の周辺に配置された引き出し配線と、
 検出電極と引き出し配線とを電気的に接続する導電性接続部とを備え、
 引き出し配線が、被めっき層にめっき触媒またはその前駆体を付与して、めっき触媒またはその前駆体が付与された被めっき層に対してめっき処理を行って金属層を形成し、金属層をパターン状にエッチングして形成される配線である、タッチパネルセンサー用導電性フィルム。
(4) 導電性接続部が、導電性ペーストまたは導電性インクを用いて印刷法により形成される接続部である、(1)~(3)のいずれかに記載のタッチパネルセンサー用導電性フィルム。
(5) 検出電極が、スパッタリング法または蒸着法により形成された電極である、(1)~(4)のいずれかに記載のタッチパネルセンサー用導電性フィルム。
(6) 基板表面に隣接してプライマー層が配置される、(1)~(5)のいずれかに記載のタッチパネルセンサー用導電性フィルム。
(7) 引き出し配線の線幅が1~10μmである、(1)~(6)のいずれかに記載のタッチパネルセンサー用導電性フィルム。
(8) (1)~(7)のいずれかに記載のタッチパネルセンサー用導電性フィルムを含む、タッチパネルセンサー。
(9) (1)~(7)のいずれかに記載のタッチパネルセンサー用導電性フィルムを含む、タッチパネル。
(1) a substrate;
A sensing electrode disposed on at least one surface of the substrate;
A patterned layer to be plated having a functional group that is arranged around the detection electrode on the surface of the substrate where the detection electrode is present and interacts with the plating catalyst or a precursor thereof;
A lead-out wiring arranged on the patterned plated layer;
A conductive connection portion for electrically connecting the detection electrode and the lead wiring;
The lead-out wiring is formed by a method having at least a step of applying a plating catalyst or a precursor thereof to the patterned plating layer and performing a plating process on the patterned plating layer to which the plating catalyst or the precursor is applied. A conductive film for a touch panel sensor, which is a connected wiring.
(2) A pattern-like to-be-plated layer gives energy to a to-be-plated layer forming composition containing the compound which has a functional group and polymeric group which interact with a plating catalyst or its precursor, in pattern shape The conductive film for a touch panel sensor according to (1), which is a layer to be formed.
(3) a substrate;
A layer to be plated having a functional group that interacts with a plating catalyst or a precursor thereof disposed on a substrate;
A sensing electrode disposed on the layer to be plated;
On the layer to be plated, the lead wiring arranged around the detection electrode,
A conductive connection portion for electrically connecting the detection electrode and the lead wiring;
The lead-out wiring gives a plating catalyst or a precursor thereof to the layer to be plated, performs a plating process on the layer to be plated to which the plating catalyst or the precursor is applied, forms a metal layer, and patterns the metal layer A conductive film for a touch panel sensor, which is a wiring formed by etching into a shape.
(4) The conductive film for a touch panel sensor according to any one of (1) to (3), wherein the conductive connection portion is a connection portion formed by a printing method using a conductive paste or conductive ink.
(5) The conductive film for a touch panel sensor according to any one of (1) to (4), wherein the detection electrode is an electrode formed by a sputtering method or a vapor deposition method.
(6) The conductive film for a touch panel sensor according to any one of (1) to (5), wherein a primer layer is disposed adjacent to the substrate surface.
(7) The conductive film for a touch panel sensor according to any one of (1) to (6), wherein the lead-out wiring has a line width of 1 to 10 μm.
(8) A touch panel sensor comprising the conductive film for a touch panel sensor according to any one of (1) to (7).
(9) A touch panel comprising the conductive film for a touch panel sensor according to any one of (1) to (7).
 本発明によれば、密着性に優れ、微細化が可能な引き出し配線を有し、引き出し配線と検出電極との電気的接続性が高いタッチパネルセンサー用導電性フィルムを提供することができる。
 また、本発明によれば、上記タッチパネルセンサー用導電性フィルムを含むタッチパネルセンサー、および、タッチパネルを提供することもできる。
ADVANTAGE OF THE INVENTION According to this invention, it can provide the conductive film for touchscreen sensors which has the lead wiring which is excellent in adhesiveness and which can be refined | miniaturized, and has high electrical connectivity with a lead wiring and a detection electrode.
Moreover, according to this invention, the touch panel sensor containing the said conductive film for touch panel sensors, and a touch panel can also be provided.
本発明のタッチパネルセンサー用導電性フィルムの第1実施形態の平面図である。It is a top view of a 1st embodiment of a conductive film for touch panel sensors of the present invention. 図1中に示した切断線A-Aに沿って切断した断面図である。FIG. 2 is a cross-sectional view taken along a cutting line AA shown in FIG. 図1中に示した切断線B-Bに沿って切断した断面図である。FIG. 2 is a cross-sectional view taken along a cutting line BB shown in FIG. 引き出し配線の製造方法の一実施形態を工程順に示す断面図である。It is sectional drawing which shows one Embodiment of the manufacturing method of extraction wiring in order of a process. 本発明のタッチパネルセンサー用導電性フィルムの第2実施形態の平面図である。It is a top view of 2nd Embodiment of the electroconductive film for touchscreen sensors of this invention. 図5中に示した切断線C-Cに沿って切断した断面図である。FIG. 6 is a cross-sectional view taken along a cutting line CC shown in FIG. 引き出し配線の製造方法の他の実施形態を工程順に示す断面図である。It is sectional drawing which shows other embodiment of the manufacturing method of extraction wiring in order of a process. 本発明のタッチパネルセンサー用導電性フィルムの第3実施形態の平面図である。It is a top view of 3rd Embodiment of the electroconductive film for touchscreen sensors of this invention. 図8中に示した切断線D-Dに沿って切断した断面図である。FIG. 9 is a cross-sectional view taken along a cutting line DD shown in FIG. 本発明のタッチパネルセンサー用導電性フィルムの第4実施形態の平面図である。It is a top view of 4th Embodiment of the electroconductive film for touchscreen sensors of this invention. 図10中に示した切断線E-Eに沿って切断した断面図である。FIG. 11 is a cross-sectional view taken along a cutting line EE shown in FIG.
 以下に、本発明のタッチパネルセンサー用導電性フィルム、タッチパネルセンサー、および、タッチパネルについて詳述する。
 なお、本明細書において「~」を用いて表される数値範囲は、「~」の前後に記載される数値を下限値および上限値として含む範囲を意味する。また、本発明における図は模式図であり、各層の厚みの関係や位置関係などは必ずしも実際のものとは一致しない。
Hereinafter, the conductive film for a touch panel sensor, the touch panel sensor, and the touch panel of the present invention will be described in detail.
In the present specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value. Further, the drawings in the present invention are schematic diagrams, and the thickness relationships and positional relationships of the layers do not necessarily match the actual ones.
 本発明のタッチパネルセンサー用導電性フィルムの特徴点の一つとしては、所定の官能基を有する被めっき層にめっき触媒またはその前駆体を付与した後、めっき処理を施して引き出し配線を形成する点、および、検出電極および引き出し配線を電気的に接合する導電性接続部を設ける点が挙げられる。
 引き出し配線の製造方法の一態様としては、所定のパターニングにより線幅の細いパターン状の被めっき層を形成した後、パターン状の被めっき層上に引き出し配線を製造することができる。つまり、引き出し配線の下地層となる被めっき層の線幅を微細化することにより、形成される引き出し配線の線幅を微細化することができる。また、引き出し配線の製造方法の他の態様として、一旦金属層を形成した後、パターン状にエッチングする態様が挙げられるが、この態様においても、エッチングの範囲を制御することにより、引き出し配線の線幅の微細化を行うことができる。
 また、被めっき層が基板と引き出し配線との間に配置されることにより、引き出し配線の密着性も優れる。
 なお、上記被めっき層を用いて引き出し配線を作製する場合、検出電極との接合性が必ずしも高くないことを本発明者らは知見した。その詳細な理由は不明だが、引き出し配線は被めっき層上に配置されるため、検出電極上に被めっき層を介して引き出し配線を形成すると被めっき層の存在により導通性が不十分となることが考えられる。また、引き出し配線上に検出電極を形成すると、被めっき層の厚みの影響によって、引き出し配線と検出電極との高さの差が生じやすく両者の接合性が低下しやすいことが考えられる。また、引き出し配線はめっき処理により形成されるため、めっき処理の際に発生しやすい不純物が引き出し配線の表面に現れ、検出電極との接合性の低下を引き起こす点なども考えられる。そこで、本発明者は、検出電極と引き出し配線とを電気的に接続する導電性接続部を設けることにより、上記問題が解決できることを見出している。
One of the features of the conductive film for a touch panel sensor of the present invention is that a plating catalyst or a precursor thereof is applied to a layer to be plated having a predetermined functional group, and then a plating process is performed to form a lead wiring. In addition, a conductive connection portion that electrically joins the detection electrode and the lead-out wiring is provided.
As one mode of the method for manufacturing the lead wiring, after forming a pattern-like plated layer with a narrow line width by predetermined patterning, the lead-out wiring can be manufactured on the pattern-like plated layer. In other words, by reducing the line width of the layer to be plated that is the base layer of the lead wiring, the line width of the lead wiring to be formed can be made fine. In addition, as another aspect of the manufacturing method of the lead wiring, there is an aspect in which a metal layer is once formed and then etched into a pattern. In this aspect, the wiring of the lead wiring can be controlled by controlling the etching range. The width can be reduced.
Further, since the layer to be plated is disposed between the substrate and the lead wiring, the adhesion of the lead wiring is also excellent.
In addition, when producing extraction wiring using the said to-be-plated layer, the present inventors discovered that joining property with a detection electrode is not necessarily high. Although the detailed reason is unknown, since the lead-out wiring is arranged on the layer to be plated, if the lead-out wiring is formed on the detection electrode via the layer to be plated, the conductivity is insufficient due to the presence of the layer to be plated. Can be considered. In addition, when the detection electrode is formed on the lead-out wiring, it is considered that the height difference between the lead-out wiring and the detection electrode is likely to occur due to the thickness of the plated layer, and the bonding property between the two is likely to be lowered. In addition, since the lead-out wiring is formed by a plating process, impurities that are likely to be generated during the plating process appear on the surface of the lead-out wiring, which may cause a decrease in bondability with the detection electrode. Therefore, the present inventors have found that the above problem can be solved by providing a conductive connection portion that electrically connects the detection electrode and the lead-out wiring.
<<第1実施形態>>
 図1に、本発明のタッチパネルセンサー用導電性フィルムの第1実施形態の平面図を示す。図2は、切断線A-Aに沿って切断した断面図である。図3は、切断線B-Bに沿って切断した断面図である。
 図1に示すように、本実施形態に係るタッチパネルセンサー用導電性フィルム10は、タッチパネルセンサーとして使用した際に使用者によって入力操作が可能な入力領域を構成する中央領域EIと、中央領域EIの外側に位置する外側領域EOとを有している。なお、中央領域とは、言い換えれば、検出電極が配置される領域であり、外側領域EOとは、言い換えれば、中央領域の外側で、引き出し配線が配置される周縁領域(周辺領域)である。
 タッチパネルセンサー用導電性フィルム10は、基板12と、基板12の一方の主面上(表面上)に配置された、検出電極14と、パターン状被めっき層16と、引き出し配線18と、導電性接続部24とを備える。検出電極14と引き出し配線18とは、導電性接続部24を介して電気的に接続している。なお、図3に示すように、引き出し配線18は、基板12の表面上に配置されたパターン状被めっき層16の上に配置される。言い換えると、基板12と引き出し配線18との間には、パターン状被めっき層16が位置する。
 以下では、上記構成について詳述する。まず、本発明の特徴点であるパターン状被めっき層16および引き出し配線18、並びに、導電性接続部24について詳述する。
<< First Embodiment >>
In FIG. 1, the top view of 1st Embodiment of the electroconductive film for touchscreen sensors of this invention is shown. FIG. 2 is a cross-sectional view taken along the cutting line AA. FIG. 3 is a cross-sectional view taken along the cutting line BB.
As shown in FIG. 1, the conductive film 10 for a touch panel sensor according to the present embodiment includes a central area E I that constitutes an input area that can be input by a user when used as a touch panel sensor, and a central area E. And an outer region E O located outside I. In addition, the central region is, in other words, a region where the detection electrode is disposed, and the outer region EO is, in other words, a peripheral region (peripheral region) where the lead-out wiring is disposed outside the central region. .
The conductive film 10 for a touch panel sensor includes a substrate 12, a detection electrode 14 disposed on one main surface (on the surface) of the substrate 12, a patterned plated layer 16, a lead-out wiring 18, and conductivity. And a connection unit 24. The detection electrode 14 and the lead wiring 18 are electrically connected via the conductive connection portion 24. As shown in FIG. 3, the lead-out wiring 18 is disposed on the patterned plated layer 16 disposed on the surface of the substrate 12. In other words, the patterned layer 16 is located between the substrate 12 and the lead wiring 18.
Below, the said structure is explained in full detail. First, the patterned plated layer 16, the lead-out wiring 18, and the conductive connection portion 24, which are the features of the present invention, will be described in detail.
[パターン状被めっき層16および引き出し配線18]
(パターン状被めっき層16)
 パターン状被めっき層16は、検出電極14の周辺(外側領域EO)に配置され、めっき触媒またはその前駆体と相互作用する官能基(以後、単に「相互作用性基」とも称する)を有するパターン状の層(被めっき層)である。パターン状被めっき層16は、相互作用性基の機能に応じて、引き出し配線を作製する際に用いるめっき触媒またはその前駆体を吸着(付着)する。つまり、パターン状被めっき層は、めっき触媒またはその前駆体の良好な受容層として機能する。
 パターン状被めっき層16は、基板12と引き出し配線18との間に位置する。つまり、パターン状被めっき層16は、引き出し配線18が配置される位置に配置される。なお、後述するように、パターン状被めっき層16の配置位置は図1の態様に限定されず、基板12上の外側領域EOの少なくとも一部(基板12上の検出電極14の周辺の少なくとも一部)に配置されていることが好ましく、外側領域EO全面にわたって配置されていてもよい。
[Pattern Layer 16 and Lead Wiring 18]
(Pattern layer 16)
The patterned plated layer 16 is disposed around the detection electrode 14 (outer region E O ) and has a functional group that interacts with the plating catalyst or its precursor (hereinafter also simply referred to as “interactive group”). It is a patterned layer (layer to be plated). The pattern-like plated layer 16 adsorbs (attaches) a plating catalyst or a precursor thereof used for producing the lead-out wiring according to the function of the interactive group. That is, the patterned plated layer functions as a good receiving layer for the plating catalyst or its precursor.
The patterned plated layer 16 is located between the substrate 12 and the lead wiring 18. That is, the patterned plated layer 16 is disposed at a position where the lead wiring 18 is disposed. As will be described later, the arrangement position of the patterned plated layer 16 is not limited to the mode of FIG. 1, and at least a part of the outer region E O on the substrate 12 (at least around the detection electrode 14 on the substrate 12). It is preferable to be disposed on a part of the outer region E 2 O.
 パターン状被めっき層16の厚みは特に制限されないが、生産性の点から、0.01~10μmが好ましく、0.2~5μmがより好ましく、0.25~1.0μmがさらに好ましい。
 また、パターン状被めっき層16の線幅は特に制限されないが、パターン状被めっき層上に配置される引き出し配線の低抵抗性の点から、30μm以下が好ましく、15μm以下がより好ましく、10μm以下がさらに好ましく、0.5μm以上が好ましく、1.0μm以上がより好ましい。
The thickness of the patterned plated layer 16 is not particularly limited, but is preferably 0.01 to 10 μm, more preferably 0.2 to 5 μm, and still more preferably 0.25 to 1.0 μm from the viewpoint of productivity.
Further, the line width of the patterned plated layer 16 is not particularly limited, but is preferably 30 μm or less, more preferably 15 μm or less, and more preferably 10 μm or less from the viewpoint of low resistance of the lead-out wiring arranged on the patterned plated layer. Is more preferable, 0.5 μm or more is preferable, and 1.0 μm or more is more preferable.
 パターン状被めっき層16に含まれる相互作用性基の種類に関しては、後段で詳述する。
 パターン状被めっき層16を構成する材料は特に制限されないが、通常、樹脂(例えば、(メタ)アクリル樹脂(架橋および非架橋の(メタ)アクリル系樹脂を含む))が挙げられ、熱硬化性樹脂または熱可塑性樹脂などの絶縁性樹脂が挙げられる。これらの材料に相互作用性基が含まれていればよい。(メタ)アクリル系樹脂とは、アクリル樹脂と、メタクリル樹脂とを含む概念である。
 より具体的には、熱硬化性樹脂としては、例えば、エポキシ樹脂、フェノール樹脂、ポリイミド樹脂、ポリエステル樹脂、ビスマレイミド樹脂、ポリオレフィン樹脂、イソシアネート樹脂、架橋(メタ)アクリル系樹脂等が挙げられる。熱可塑性樹脂としては、例えば、フェノキシ樹脂、ポリエーテルスルフォン、ポリスルフォン、ポリフェニレンスルフォン、ポリフェニレンサルファイド、ポリフェニルエーテル、ポリエーテルイミド、非架橋の(メタ)アクリル系樹脂等が挙げられる。
The type of the interactive group contained in the patterned plated layer 16 will be described in detail later.
Although the material which comprises the pattern-like to-be-plated layer 16 is not restrict | limited in particular, Usually, resin (For example, (meth) acrylic resin (a bridge | crosslinking and non-crosslinking (meth) acrylic resin is included)) is mentioned, Thermosetting Examples thereof include an insulating resin such as a resin or a thermoplastic resin. These materials only need to contain an interactive group. The (meth) acrylic resin is a concept including an acrylic resin and a methacrylic resin.
More specifically, examples of the thermosetting resin include epoxy resins, phenol resins, polyimide resins, polyester resins, bismaleimide resins, polyolefin resins, isocyanate resins, and crosslinked (meth) acrylic resins. Examples of the thermoplastic resin include phenoxy resin, polyether sulfone, polysulfone, polyphenylene sulfone, polyphenylene sulfide, polyphenyl ether, polyether imide, and non-crosslinked (meth) acrylic resin.
 パターン状被めっき層16の形成方法は、所定の相互作用性基を有するパターン状の層が形成されれば特に制限されないが、後述する被めっき層形成用組成物を使用する態様が好適に挙げられる。 The method of forming the patterned plated layer 16 is not particularly limited as long as a patterned layer having a predetermined interactive group is formed, but an embodiment using a composition for forming a plated layer to be described later is preferable. It is done.
(引き出し配線18)
 引き出し配線18は、検出電極14に電圧を印加するための役割を担う部材である。引き出し配線18は、基板12上の外側領域EOに配置され、その一端が対応する検出電極14に導電性接続部24を介して電気的に接続され、その他端はフレキシブルプリント配線板などが配置される場所に位置している。
 なお、図1においては、引き出し配線18は5本記載されているが、その数は特に制限されず、通常、検出電極14の数に応じて複数配置される。
(Leader wiring 18)
The lead wiring 18 is a member that plays a role in applying a voltage to the detection electrode 14. The lead-out wiring 18 is disposed in the outer region EO on the substrate 12, one end thereof is electrically connected to the corresponding detection electrode 14 through the conductive connection portion 24, and the other end is disposed with a flexible printed wiring board or the like. Is located in a place.
In FIG. 1, five lead wires 18 are shown, but the number is not particularly limited, and a plurality of lead wires 18 are usually arranged according to the number of detection electrodes 14.
 引き出し配線18の厚みは特に制限されず、使用目的に応じ適宜最適な厚みが選択されるが、導電特性の点から、0.1μm以上であることが好ましく、0.5μm以上であることが好ましく、1~30μmがより好ましい。
 引き出し配線18の線幅は特に制限されないが、引き出し配線の低抵抗性の点から、30μm以下が好ましく、15μm以下がより好ましく、10μm以下がさらに好ましく、0.5μm以上が好ましく、1.0μm以上がより好ましい。
 また、引き出し配線18を構成する金属の種類は特に制限されず、例えば、銅、クロム、鉛、ニッケル、金、銀、すず、亜鉛などが挙げられ、導電性の観点から、銅、金、銀が好ましく、銅、銀がより好ましい。
The thickness of the lead-out wiring 18 is not particularly limited, and an optimum thickness is appropriately selected according to the purpose of use, but is preferably 0.1 μm or more and preferably 0.5 μm or more from the viewpoint of conductive characteristics. 1 to 30 μm is more preferable.
The line width of the lead wiring 18 is not particularly limited, but is preferably 30 μm or less, more preferably 15 μm or less, further preferably 10 μm or less, more preferably 0.5 μm or more, and 1.0 μm or more from the viewpoint of low resistance of the lead wiring Is more preferable.
Further, the type of metal constituting the lead wiring 18 is not particularly limited, and examples thereof include copper, chromium, lead, nickel, gold, silver, tin, and zinc. From the viewpoint of conductivity, copper, gold, silver Are preferable, and copper and silver are more preferable.
(パターン状被めっき層および引き出し配線の製造方法)
 パターン状被めっき層16および引き出し配線18の製造方法は特に制限されないが、形成される引き出し配線18の微細化がしやすい点で、基板上にパターン状被めっき層を形成する工程(工程1)と、パターン状被めっき層上に引き出し配線を形成する工程(工程2)とを実施することが好ましい。
 以下、各工程で使用される部材・材料、および、その手順について詳述する。
(Pattern-like plated layer and lead wiring manufacturing method)
The manufacturing method of the patterned plated layer 16 and the lead wiring 18 is not particularly limited, but the step of forming the patterned plated layer on the substrate is easy in that the formed lead wiring 18 is easily miniaturized (step 1). It is preferable to carry out the step (step 2) of forming the lead wiring on the patterned layer to be plated.
Hereinafter, members and materials used in each process and the procedure thereof will be described in detail.
[工程1:パターン状被めっき層形成工程]
 工程1は、めっき触媒またはその前駆体と相互作用する官能基および重合性基を有する化合物を含有する被めっき層形成用組成物にパターン状にエネルギーを付与して、パターン状被めっき層を基板上に形成する工程である。より具体的には、まず、図4(A)に示すように、基板12上に被めっき層形成用組成物の塗膜20を形成し、図4(B)に示すように、得られた塗膜20に対して黒矢印で示すようにパターン状にエネルギーを付与することにより重合性基の反応を促進させて硬化し、次に、エネルギーが付与されなかった領域を除去してパターン状被めっき層16を得る工程(図4(C))である。
 上記工程によって形成されるパターン状被めっき層16は、相互作用性基の機能に応じて、後述する工程2でめっき触媒またはその前駆体を吸着(付着)する。また、重合性基は、エネルギー付与による硬化処理によって化合物同士の結合に利用され、硬さ・硬度に優れたパターン状被めっき層16を得ることができる。
 以下では、まず、本工程で使用される材料について詳述し、その後、工程の手順について詳述する。なお、使用される基板に関しては、後段で詳述する。
[Step 1: Patterned plating layer forming step]
In step 1, energy is applied in a pattern to a composition for forming a plating layer containing a compound having a functional group and a polymerizable group that interacts with the plating catalyst or its precursor, and the patterned plating layer is formed into a substrate. It is a process of forming on top. More specifically, first, as shown in FIG. 4 (A), a coating film 20 of the composition for forming a layer to be plated was formed on the substrate 12, and obtained as shown in FIG. 4 (B). By applying energy to the coating film 20 as indicated by the black arrows, the reaction of the polymerizable group is promoted to cure, and then the region to which no energy has been applied is removed to remove the pattern covering. This is a step (FIG. 4C) for obtaining the plating layer 16.
The patterned plated layer 16 formed by the above process adsorbs (attaches) the plating catalyst or its precursor in the process 2 to be described later according to the function of the interactive group. Moreover, a polymeric group is utilized for the coupling | bonding of compounds by the hardening process by energy provision, and can obtain the pattern-like to-be-plated layer 16 excellent in hardness and hardness.
Below, the material used at this process is explained in full detail first, and the procedure of a process is explained in full detail after that. The substrate to be used will be described in detail later.
(被めっき層形成用組成物)
 被めっき層形成用組成物には、相互作用性基および重合性基を有する化合物が含有される。
 相互作用性基とは、後述する工程でパターン状被めっき層に付与されるめっき触媒またはその前駆体と相互作用できる官能基を意図し、例えば、めっき触媒またはその前駆体と静電相互作用を形成可能な官能基、または、めっき触媒またはその前駆体と配位形成可能な含窒素官能基、含硫黄官能基、含酸素官能基などを使用することができる。
 相互作用性基としてより具体的には、アミノ基、アミド基、イミド基、ウレア基、3級のアミノ基、アンモニウム基、アミジノ基、トリアジン環、トリアゾール環、ベンゾトリアゾール基、イミダゾール基、ベンズイミダゾール基、キノリン基、ピリジン基、ピリミジン基、ピラジン基、ナゾリン基、キノキサリン基、プリン基、トリアジン基、ピペリジン基、ピペラジン基、ピロリジン基、ピラゾール基、アニリン基、アルキルアミン構造を含む基、イソシアヌル構造を含む基、ニトロ基、ニトロソ基、アゾ基、ジアゾ基、アジド基、シアノ基、シアネート基(R-O-CN)などの含窒素官能基;エーテル基、水酸基、フェノール性水酸基、カルボキシル基、カーボネート基、カルボニル基、エステル基、N-オキシド構造を含む基、S-オキシド構造を含む基、N-ヒドロキシ構造を含む基などの含酸素官能基;チオフェン基、チオール基、チオウレア基、チオシアヌール酸基、ベンズチアゾール基、メルカプトトリアジン基、チオエーテル基、チオキシ基、スルホキシド基、スルホン基、サルファイト基、スルホキシイミン構造を含む基、スルホキシニウム塩構造を含む基、スルホン酸基、スルホン酸エステル構造を含む基などの含硫黄官能基;ホスフォート基、ホスフォロアミド基、ホスフィン基、リン酸エステル構造を含む基などの含リン官能基;塩素、臭素などのハロゲン原子を含む基などが挙げられ、塩構造をとりうる官能基においてはそれらの塩も使用することができる。
 なかでも、極性が高く、めっき触媒またはその前駆体などへの吸着能が高いことから、カルボキシル基、スルホン酸基、リン酸基、およびボロン酸基などのイオン性極性基や、エーテル基、またはシアノ基が好ましく、カルボキシル基またはシアノ基がより好ましい。
 化合物中には、相互作用性基が2種以上含まれていてもよい。また、化合物中に含まれる相互作用性基の数は特に制限されず、1つでも、2つ以上でもよい。
(Composition for plating layer formation)
The composition for forming a layer to be plated contains a compound having an interactive group and a polymerizable group.
The interactive group is intended to mean a functional group capable of interacting with a plating catalyst or a precursor thereof applied to the patterned plating layer in a process described later. For example, an electrostatic interaction with the plating catalyst or a precursor thereof is performed. A functional group that can be formed, or a nitrogen-containing functional group, a sulfur-containing functional group, an oxygen-containing functional group, and the like that can be coordinated with a plating catalyst or a precursor thereof can be used.
More specifically, as an interactive group, amino group, amide group, imide group, urea group, tertiary amino group, ammonium group, amidino group, triazine ring, triazole ring, benzotriazole group, imidazole group, benzimidazole Group, quinoline group, pyridine group, pyrimidine group, pyrazine group, nazoline group, quinoxaline group, purine group, triazine group, piperidine group, piperazine group, pyrrolidine group, pyrazole group, aniline group, group containing alkylamine structure, isocyanuric structure Nitrogen-containing functional groups such as nitro group, nitroso group, azo group, diazo group, azide group, cyano group, cyanate group (R—O—CN); ether group, hydroxyl group, phenolic hydroxyl group, carboxyl group, Carbonate group, carbonyl group, ester group, group containing N-oxide structure, S Oxygen-containing functional groups such as a group containing an oxide structure and a group containing an N-hydroxy structure; Sulfur-containing functional groups such as sulfone group, sulfite group, group containing sulfoxyimine structure, group containing sulfoxynium salt structure, sulfonic acid group, group containing sulfonic acid ester structure; Phosphate group, phosphoramide group, phosphine group And a phosphorus-containing functional group such as a group containing a phosphate ester structure; a group containing a halogen atom such as chlorine and bromine, and the like. In a functional group capable of taking a salt structure, a salt thereof can also be used.
Among them, since the polarity is high and the adsorption ability to a plating catalyst or a precursor thereof is high, an ionic polar group such as a carboxyl group, a sulfonic acid group, a phosphoric acid group, and a boronic acid group, an ether group, or A cyano group is preferable, and a carboxyl group or a cyano group is more preferable.
Two or more types of interactive groups may be contained in the compound. The number of interactive groups contained in the compound is not particularly limited, and may be one or two or more.
 重合性基は、エネルギー付与により、化学結合を形成しうる官能基であり、例えば、ラジカル重合性基、カチオン重合性基などが挙げられる。なかでも、反応性がより優れる点から、ラジカル重合性基が好ましい。ラジカル重合性基としては、例えば、アクリル酸エステル基(アクリロイルオキシ基)、メタクリル酸エステル基(メタクリロイルオキシ基)、イタコン酸エステル基、クロトン酸エステル基、イソクロトン酸エステル基、マレイン酸エステル基などの不飽和カルボン酸エステル基、スチリル基、ビニル基、アクリルアミド基、メタクリルアミド基などが挙げられる。なかでも、メタクリロイルオキシ基、アクリロイルオキシ基、ビニル基、スチリル基、アクリルアミド基、メタクリルアミド基が好ましく、メタクリロイルオキシ基、アクリロイルオキシ基、スチリル基が特に好ましい。
 化合物中には、重合性基が2種以上含まれていてもよい。また、化合物中に含まれる重合性基の数は特に制限されず、1つでも、2つ以上でもよい。
The polymerizable group is a functional group that can form a chemical bond by applying energy, and examples thereof include a radical polymerizable group and a cationic polymerizable group. Among these, a radical polymerizable group is preferable from the viewpoint of more excellent reactivity. Examples of radical polymerizable groups include acrylic acid ester groups (acryloyloxy groups), methacrylic acid ester groups (methacryloyloxy groups), itaconic acid ester groups, crotonic acid ester groups, isocrotonic acid ester groups, maleic acid ester groups, and the like. Examples include unsaturated carboxylic acid ester groups, styryl groups, vinyl groups, acrylamide groups, and methacrylamide groups. Of these, a methacryloyloxy group, an acryloyloxy group, a vinyl group, a styryl group, an acrylamide group, and a methacrylamide group are preferable, and a methacryloyloxy group, an acryloyloxy group, and a styryl group are particularly preferable.
Two or more polymerizable groups may be contained in the compound. The number of polymerizable groups contained in the compound is not particularly limited, and may be one or two or more.
 上記化合物は、低分子化合物であっても、高分子化合物であってもよい。低分子化合物は分子量が1000未満の化合物を意図し、高分子化合物とは分子量が1000以上の化合物を意図する。
 なお、上記重合性基を有する低分子化合物とは、いわゆるモノマー(単量体)に該当する。また、高分子化合物とは、所定の繰り返し単位を有するポリマーであってもよい。
 また、化合物としては1種のみを使用してもよいし、2種以上を併用してもよい。
The compound may be a low molecular compound or a high molecular compound. A low molecular weight compound intends a compound having a molecular weight of less than 1000, and a high molecular weight compound intends a compound having a molecular weight of 1000 or more.
The low molecular compound having a polymerizable group corresponds to a so-called monomer. The polymer compound may be a polymer having a predetermined repeating unit.
Moreover, as a compound, only 1 type may be used and 2 or more types may be used together.
 上記化合物がポリマーである場合、ポリマーの重量平均分子量は特に制限されないが、溶解性など取扱い性がより優れる点で、1000以上70万以下が好ましく、さらに好ましくは2000以上20万以下である。特に、重合感度の観点から、20000以上であることが好ましい。
 このような重合性基および相互作用性基を有するポリマーの合成方法は特に制限されず、公知の合成方法(特許公開2009-280905号の段落[0097]~[0125]参照)が使用される。
When the compound is a polymer, the weight average molecular weight of the polymer is not particularly limited, but is preferably 1000 or more and 700,000 or less, and more preferably 2000 or more and 200,000 or less, from the viewpoint of better handleability such as solubility. In particular, from the viewpoint of polymerization sensitivity, it is preferably 20000 or more.
The method for synthesizing such a polymer having a polymerizable group and an interactive group is not particularly limited, and a known synthesis method (see paragraphs [0097] to [0125] of Patent Publication 2009-280905) is used.
(ポリマーの好適態様1)
 ポリマーの第1の好ましい態様として、下記式(a)で表される重合性基を有する繰り返し単位(以下、適宜重合性基ユニットとも称する)、および、下記式(b)で表される相互作用性基を有する繰り返し単位(以下、適宜相互作用性基ユニットとも称する)を含む共重合体が挙げられる。
(Preferred embodiment 1 of polymer)
As a first preferred embodiment of the polymer, a repeating unit having a polymerizable group represented by the following formula (a) (hereinafter also referred to as a polymerizable group unit as appropriate) and an interaction represented by the following formula (b) And a copolymer containing a repeating unit having a functional group (hereinafter also referred to as an interactive group unit as appropriate).
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000001
 上記式(a)および式(b)中、R1~R5は、それぞれ独立して、水素原子、または、置換若しくは無置換のアルキル基(例えば、メチル基、エチル基、プロピル基、ブチル基など)を表す。なお、置換基の種類は特に制限されないが、メトキシ基、塩素原子、臭素原子、またはフッ素原子などが挙げられる。
 なお、R1としては、水素原子、メチル基、または、臭素原子で置換されたメチル基が好ましい。R2としては、水素原子、メチル基、または、臭素原子で置換されたメチル基が好ましい。R3としては、水素原子が好ましい。R4としては、水素原子が好ましい。R5としては、水素原子、メチル基、または、臭素原子で置換されたメチル基が好ましい。
In the above formulas (a) and (b), R 1 to R 5 are each independently a hydrogen atom or a substituted or unsubstituted alkyl group (for example, a methyl group, an ethyl group, a propyl group, a butyl group) Etc.). The kind of the substituent is not particularly limited, and examples thereof include a methoxy group, a chlorine atom, a bromine atom, or a fluorine atom.
R 1 is preferably a hydrogen atom, a methyl group, or a methyl group substituted with a bromine atom. R 2 is preferably a hydrogen atom, a methyl group, or a methyl group substituted with a bromine atom. R 3 is preferably a hydrogen atom. R 4 is preferably a hydrogen atom. R 5 is preferably a hydrogen atom, a methyl group, or a methyl group substituted with a bromine atom.
 上記式(a)および式(b)中、X、Y、およびZは、それぞれ独立して、単結合、または、置換若しく無置換の2価の有機基を表す。2価の有機基としては、置換若しくは無置換の2価の脂肪族炭化水素基(好ましくは炭素数1~8。例えば、メチレン基、エチレン基、プロピレン基などのアルキレン基)、置換若しくは無置換の2価の芳香族炭化水素基(好ましくは炭素数6~12。例えば、フェニレン基)、-O-、-S-、-SO2-、-N(R)-(R:アルキル基)、-CO-、-NH-、-COO-、-CONH-、またはこれらを組み合わせた基(例えば、アルキレンオキシ基、アルキレンオキシカルボニル基、アルキレンカルボニルオキシ基など)などが挙げられる。 In the above formulas (a) and (b), X, Y, and Z each independently represent a single bond or a substituted or unsubstituted divalent organic group. Examples of the divalent organic group include a substituted or unsubstituted divalent aliphatic hydrocarbon group (preferably having 1 to 8 carbon atoms, for example, an alkylene group such as a methylene group, an ethylene group, and a propylene group), a substituted or unsubstituted group. A divalent aromatic hydrocarbon group (preferably having 6 to 12 carbon atoms, such as a phenylene group), —O—, —S—, —SO 2 —, —N (R) — (R: alkyl group), And —CO—, —NH—, —COO—, —CONH—, or a combination thereof (for example, an alkyleneoxy group, an alkyleneoxycarbonyl group, an alkylenecarbonyloxy group, and the like).
 X、Y、およびZとしては、ポリマーの合成が容易で、引き出し配線の密着性がより優れる点で、単結合、エステル基(-COO-)、アミド基(-CONH-)、エーテル基(-O-)、または置換若しくは無置換の2価の芳香族炭化水素基が好ましく、単結合、エステル基(-COO-)、アミド基(-CONH-)がより好ましい。 As X, Y, and Z, a single bond, ester group (—COO—), amide group (—CONH—), ether group (— O—) or a substituted or unsubstituted divalent aromatic hydrocarbon group is preferable, and a single bond, an ester group (—COO—), or an amide group (—CONH—) is more preferable.
 上記式(a)および式(b)中、L1およびL2は、それぞれ独立して、単結合、または、置換若しくは無置換の2価の有機基を表す。2価の有機基の定義としては、上述したX、Y、およびZで述べた2価の有機基と同義である。
 L1としては、ポリマーの合成が容易で、引き出し配線の密着性がより優れる点で、脂肪族炭化水素基、または、ウレタン結合若しくはウレア結合を有する2価の有機基(例えば、脂肪族炭化水素基)が好ましく、なかでも、総炭素数1~9であるものが好ましい。なお、ここで、L1の総炭素数とは、L1で表される置換または無置換の2価の有機基に含まれる総炭素原子数を意味する。
In the above formulas (a) and (b), L 1 and L 2 each independently represent a single bond or a substituted or unsubstituted divalent organic group. As a definition of a divalent organic group, it is synonymous with the divalent organic group described by X, Y, and Z mentioned above.
L 1 is an aliphatic hydrocarbon group or a divalent organic group having a urethane bond or a urea bond (for example, an aliphatic hydrocarbon) in that the polymer is easily synthesized and the adhesion of the lead wiring is more excellent. Group), and those having a total carbon number of 1 to 9 are preferred. Incidentally, the total number of carbon atoms of L 1, means the total number of carbon atoms contained in the divalent organic group or a substituted or unsubstituted represented by L 1.
 また、L2は、引き出し配線の密着性がより優れる点で、単結合、または、2価の脂肪族炭化水素基、2価の芳香族炭化水素基、もしくはこれらを組み合わせた基であることが好ましい。なかでも、L2は、単結合、または、総炭素数が1~15であることが好ましく、特に無置換であることが好ましい。なお、ここで、L2の総炭素数とは、L2で表される置換または無置換の2価の有機基に含まれる総炭素原子数を意味する。 L 2 may be a single bond, a divalent aliphatic hydrocarbon group, a divalent aromatic hydrocarbon group, or a combination of these in terms of better adhesion of the lead-out wiring. preferable. Among these, L 2 preferably has a single bond or a total carbon number of 1 to 15, and is particularly preferably unsubstituted. Incidentally, the total number of carbon atoms of L 2, means the total number of carbon atoms contained in the divalent organic group or a substituted or unsubstituted represented by L 2.
 上記式(b)中、Wは、相互作用性基を表す。相互作用性基の定義は、上述の通りである。 In the above formula (b), W represents an interactive group. The definition of the interactive group is as described above.
 上記重合性基ユニットの含有量は、反応性(硬化性、重合性)および合成の際のゲル化の抑制の点から、ポリマー中の全繰り返し単位に対して、5~50モル%が好ましく、5~40モル%がより好ましい。
 また、上記相互作用性基ユニットの含有量は、めっき触媒またはその前駆体に対する吸着性の観点から、ポリマー中の全繰り返し単位に対して、5~95モル%が好ましく、10~95モル%がより好ましい。
The content of the polymerizable group unit is preferably 5 to 50 mol% with respect to all repeating units in the polymer from the viewpoint of reactivity (curability, polymerization) and suppression of gelation during synthesis, 5 to 40 mol% is more preferable.
In addition, the content of the interactive group unit is preferably 5 to 95 mol%, preferably 10 to 95 mol%, based on all repeating units in the polymer, from the viewpoint of adsorptivity to the plating catalyst or its precursor. More preferred.
(ポリマーの好適態様2)
 ポリマーの第2の好ましい態様としては、下記式(A)、式(B)、および式(C)で表される繰り返し単位を含む共重合体が挙げられる
(Preferred embodiment 2 of polymer)
As a 2nd preferable aspect of a polymer, the copolymer containing the repeating unit represented by a following formula (A), a formula (B), and a formula (C) is mentioned.
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
 式(A)で表される繰り返し単位は上記式(a)で表される繰り返し単位と同じであり、各基の説明も同じである。
 式(B)で表される繰り返し単位中のR5、XおよびL2は、上記式(b)で表される繰り返し単位中のR5、XおよびL2と同じであり、各基の説明も同じである。
 式(B)中のWaは、後述するVで表される親水性基またはその前駆体基を除く、めっき触媒またはその前駆体と相互作用する基を表す。なかでも、シアノ基、エーテル基が好ましい。
The repeating unit represented by the formula (A) is the same as the repeating unit represented by the above formula (a), and the description of each group is also the same.
R 5, X and L 2 in the repeating unit represented by formula (B) is the same as R 5, X and L 2 in the repeating unit represented by formula (b), a description of each group Is the same.
Wa in the formula (B) represents a group that interacts with the plating catalyst or its precursor, excluding the hydrophilic group represented by V described later or its precursor group. Of these, a cyano group and an ether group are preferable.
 式(C)中、R6は、それぞれ独立して、水素原子、または、置換若しくは無置換のアルキル基を表す。
 式(C)中、Uは、単結合、または、置換若しく無置換の2価の有機基を表す。2価の有機基の定義は、上述したX、YおよびZで表される2価の有機基と同義である。Uとしては、ポリマーの合成が容易で、引き出し配線の密着性がより優れる点で、単結合、エステル基(-COO-)、アミド基(-CONH-)、エーテル基(-O-)、または置換若しくは無置換の2価の芳香族炭化水素基が好ましい。
 式(C)中、L3は、単結合、または、置換若しく無置換の2価の有機基を表す。2価の有機基の定義は、上述したL1およびL2で表される2価の有機基と同義である。L3としては、ポリマーの合成が容易で、引き出し配線の密着性がより優れる点で、単結合、または、2価の脂肪族炭化水素基、2価の芳香族炭化水素基、またはこれらを組み合わせた基であることが好ましい。
In formula (C), each R 6 independently represents a hydrogen atom or a substituted or unsubstituted alkyl group.
In formula (C), U represents a single bond or a substituted or unsubstituted divalent organic group. The definition of a bivalent organic group is synonymous with the divalent organic group represented by X, Y, and Z mentioned above. U is a single bond, an ester group (—COO—), an amide group (—CONH—), an ether group (—O—), or an ether group in that the synthesis of the polymer is easy and the adhesion of the lead wiring is more excellent. A substituted or unsubstituted divalent aromatic hydrocarbon group is preferred.
In Formula (C), L 3 represents a single bond or a substituted or unsubstituted divalent organic group. The definition of a divalent organic group is synonymous with the divalent organic group represented by L 1 and L 2 described above. L 3 is a single bond, a divalent aliphatic hydrocarbon group, a divalent aromatic hydrocarbon group, or a combination thereof in that the polymer is easily synthesized and the adhesion of the lead-out wiring is better. It is preferable that
 式(C)中、Vは親水性基またはその前駆体基を表す。親水性基とは親水性を示す基であれば特に限定されず、例えば、水酸基、カルボン酸基などが挙げられる。また、親水性基の前駆体基とは、所定の処理(例えば、酸またはアルカリにより処理)により親水性基を生じる基を意味し、例えば、THP(2-テトラヒドロピラニル基)で保護したカルボキシル基などが挙げられる。
 親水性基としては、めっき触媒またはその前駆体との相互作用の点で、イオン性極性基であることが好ましい。イオン性極性基としては、具体的には、カルボン酸基、スルホン酸基、リン酸基、ボロン酸基が挙げられる。なかでも、適度な酸性(他の官能基を分解しない)という点から、カルボン酸基が好ましい。
In the formula (C), V represents a hydrophilic group or a precursor group thereof. The hydrophilic group is not particularly limited as long as it is a hydrophilic group, and examples thereof include a hydroxyl group and a carboxylic acid group. The precursor group of the hydrophilic group means a group that generates a hydrophilic group by a predetermined treatment (for example, treatment with acid or alkali). For example, a carboxyl group protected with THP (2-tetrahydropyranyl group) Group and the like.
The hydrophilic group is preferably an ionic polar group in terms of interaction with the plating catalyst or its precursor. Specific examples of the ionic polar group include a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, and a boronic acid group. Among these, a carboxylic acid group is preferable from the viewpoint of moderate acidity (does not decompose other functional groups).
 上記ポリマーの第2の好ましい態様における各ユニットの好ましい含有量は、以下の通りである。
 式(A)で表される繰り返し単位の含有量は、反応性(硬化性、重合性)および合成の際のゲル化の抑制の点から、ポリマー中の全繰り返し単位に対して、5~50モル%が好ましく、5~30モル%がより好ましい。
 式(B)で表される繰り返し単位の含有量は、めっき触媒またはその前駆体に対する吸着性の観点から、ポリマー中の全繰り返し単位に対して、5~75モル%が好ましく、10~70モル%がより好ましい。
 式(C)で表される繰り返し単位の含有量は、水溶液による現像性と耐湿密着性の点から、ポリマー中の全繰り返し単位に対して、10~70モル%が好ましく、20~60モル%がより好ましく、30~50モル%がさらに好ましい。
The preferred content of each unit in the second preferred embodiment of the polymer is as follows.
The content of the repeating unit represented by the formula (A) is 5 to 50 with respect to all the repeating units in the polymer from the viewpoint of reactivity (curability, polymerizability) and suppression of gelation during synthesis. The mol% is preferable, and 5 to 30 mol% is more preferable.
The content of the repeating unit represented by the formula (B) is preferably 5 to 75 mol% with respect to all the repeating units in the polymer, from the viewpoint of adsorptivity to the plating catalyst or its precursor, and 10 to 70 mol. % Is more preferable.
The content of the repeating unit represented by the formula (C) is preferably from 10 to 70 mol%, preferably from 20 to 60 mol%, based on all repeating units in the polymer, from the viewpoints of developability with an aqueous solution and moisture-resistant adhesion. Is more preferable, and 30 to 50 mol% is more preferable.
 上記ポリマーの具体例としては、例えば、特開2009-007540号公報の段落[0106]~[0112]に記載のポリマー、特開2006-135271号公報の段落[0065]~[0070]に記載のポリマー、US2010-080964号の段落[0030]~[0108]に記載のポリマーなどが挙げられる。
 このポリマーは、公知の方法(例えば、上記で列挙された文献中の方法)により製造することができる。
Specific examples of the polymer include, for example, polymers described in paragraphs [0106] to [0112] of JP-A-2009-007540, and paragraphs [0065] to [0070] of JP-A-2006-135271. Examples thereof include polymers described in paragraphs [0030] to [0108] of US2010-080964.
The polymer can be prepared by known methods (eg, the methods in the literature listed above).
(モノマーの好適態様)
 上記化合物がいわゆるモノマーである場合、好適態様の一つとして式(X)で表される化合物が挙げられる。
(Preferred embodiment of monomer)
When the said compound is what is called a monomer, the compound represented by Formula (X) is mentioned as one of the suitable aspects.
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
 式(X)中、R11~R13は、それぞれ独立して、水素原子、または置換若しくは無置換のアルキル基を表す。無置換のアルキル基としては、メチル基、エチル基、プロピル基、またはブチル基が挙げられる。また、置換アルキル基としては、メトキシ基、塩素原子、臭素原子、またはフッ素原子等で置換された、メチル基、エチル基、プロピル基、ブチル基が挙げられる。なお、R11としては、水素原子、またはメチル基が好ましい。R12としては、水素原子が好ましい。R13としては、水素原子が好ましい。 In the formula (X), R 11 to R 13 each independently represents a hydrogen atom or a substituted or unsubstituted alkyl group. 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 methyl group, an ethyl group, a propyl group, and a butyl group substituted with a methoxy group, a chlorine atom, a bromine atom, or a fluorine atom. R 11 is preferably a hydrogen atom or a methyl group. R 12 is preferably a hydrogen atom. R 13 is preferably a hydrogen atom.
 L10は、単結合、または、2価の有機基を表す。2価の有機基としては、置換若しくは無置換の脂肪族炭化水素基(好ましくは炭素数1~8)、置換若しくは無置換の芳香族炭化水素基(好ましくは炭素数6~12)、-O-、-S-、-SO2-、-N(R)-(R:アルキル基)、-CO-、-NH-、-COO-、-CONH-、またはこれらを組み合わせた基(例えば、アルキレンオキシ基、アルキレンオキシカルボニル基、アルキレンカルボニルオキシ基など)などが挙げられる。
 置換または無置換の脂肪族炭化水素基としては、メチレン基、エチレン基、プロピレン基、若しくはブチレン基、または、これらの基が、メトキシ基、塩素原子、臭素原子、若しくはフッ素原子等で置換されたものが好ましい。
 置換または無置換の芳香族炭化水素基としては、無置換のフェニレン基、または、メトキシ基、塩素原子、臭素原子、若しくはフッ素原子等で置換されたフェニレン基が好ましい。
 式(X)中、L10の好適態様の一つとしては、-NH-脂肪族炭化水素基-、または、-CO-脂肪族炭化水素基-が挙げられる。
L 10 represents a single bond or a divalent organic group. Examples of the divalent organic group include a substituted or unsubstituted aliphatic hydrocarbon group (preferably having 1 to 8 carbon atoms), a substituted or unsubstituted aromatic hydrocarbon group (preferably having 6 to 12 carbon atoms), —O —, —S—, —SO 2 —, —N (R) — (R: alkyl group), —CO—, —NH—, —COO—, —CONH—, or a combination thereof (for example, alkylene Oxy group, alkyleneoxycarbonyl group, alkylenecarbonyloxy group, etc.).
As a substituted or unsubstituted aliphatic hydrocarbon group, a methylene group, an ethylene group, a propylene group, or a butylene group, or these groups are substituted with a methoxy group, a chlorine atom, a bromine atom, a fluorine atom, or the like Those are preferred.
As the substituted or unsubstituted aromatic hydrocarbon group, an unsubstituted phenylene group or a phenylene group substituted with a methoxy group, a chlorine atom, a bromine atom, a fluorine atom or the like is preferable.
In Formula (X), one preferred embodiment of L 10 includes —NH—aliphatic hydrocarbon group— or —CO—aliphatic hydrocarbon group—.
 Wの定義は、式(b)中のWの定義の同義であり、相互作用性基を表す。相互作用性基の定義は、上述の通りである。
 式(X)中、Wの好適態様としては、イオン性極性基が挙げられ、カルボン酸基がより好ましい。
The definition of W is synonymous with the definition of W in Formula (b), and represents an interactive group. The definition of the interactive group is as described above.
In Formula (X), as a suitable aspect of W, an ionic polar group is mentioned, A carboxylic acid group is more preferable.
 上記化合物がいわゆるモノマーである場合、他の好適態様の一つとして式(1)で表される化合物が挙げられる。 When the compound is a so-called monomer, another preferred embodiment is a compound represented by the formula (1).
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004
 式(1)中、R10は、水素原子、金属カチオン、または第四級アンモニウムカチオンを表す。金属カチオンとしては、例えば、アルカリ金属カチオン(ナトリウムイオン、カルシウムイオン)、銅イオン、パラジウムイオン、銀イオンなどが挙げられる。なお、金属カチオンとしては、主に1価または2価のものが使用され、2価のもの(例えば、パラジウムイオン)が使用される場合、後述するnは2を表す。
 第四級アンモニウムカチオンとしては、例えば、テトラメチルアンモニウムイオン、テトラブチルアンモニウムイオンなどが挙げられる。
 なかでも、めっき触媒またはその前駆体の付着、および、パターニング後の金属残渣の点から、水素原子であることが好ましい。
In formula (1), R 10 represents a hydrogen atom, a metal cation, or a quaternary ammonium cation. Examples of metal cations include alkali metal cations (sodium ions, calcium ions), copper ions, palladium ions, silver ions, and the like. In addition, as a metal cation, a monovalent or bivalent thing is mainly used, and when bivalent thing (for example, palladium ion) is used, n mentioned later represents 2.
Examples of the quaternary ammonium cation include tetramethylammonium ion and tetrabutylammonium ion.
Especially, it is preferable that it is a hydrogen atom from the point of adhesion of a plating catalyst or its precursor, and the metal residue after patterning.
 式(1)中のL10の定義は、上述した式(X)中のL10の定義と同義であり、単結合、または、2価の有機基を表す。2価の有機基の定義は、上述の通りである。 Defining L 10 in the formula (1) are the same as defined in L 10 in the above-mentioned formula (X), a single bond, or a divalent organic group. The definition of the divalent organic group is as described above.
 式(1)中のR11~R13の定義は、上述した式(X)中のR11~R13の定義と同義であり、水素原子、または置換若しくは無置換のアルキル基を表す。なお、R11~R13の好適態様は上述の通りである。
 nは、1または2の整数を表す。なかでも、化合物の入手性の観点から、nは1であることが好ましい。
Definition of R 11 ~ R 13 in the formula (1) has the same meaning as the definition of R 11 ~ R 13 in the above-mentioned formula (X), represents a hydrogen atom or a substituted or unsubstituted alkyl group,. The preferred embodiments of R 11 to R 13 are as described above.
n represents an integer of 1 or 2. Especially, it is preferable that n is 1 from a viewpoint of the availability of a compound.
 式(1)で表される化合物の好適態様として、式(2)で表される化合物が挙げられる。 As a preferred embodiment of the compound represented by the formula (1), a compound represented by the formula (2) may be mentioned.
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000005
 式(2)中、R10、R11およびnは、上記の定義と同じである。
 L11は、エステル基(-COO-)、アミド基(-CONH-)、またはフェニレン基を表す。なかでも、L11がアミド基であると、得られる被めっき層の重合性、および、耐溶剤性(例えば、アルカリ溶剤耐性)が向上する。
 L12は、単結合、2価の脂肪族炭化水素基(好ましくは炭素数1~8、より好ましくは炭素数3~5)、または、2価の芳香族炭化水素基を表す。脂肪族炭化水素基は、直鎖状、分岐状、環状であってもよい。なお、L12が単結合の場合、L11はフェニレン基を表す。 
In formula (2), R 10 , R 11 and n are the same as defined above.
L 11 represents an ester group (—COO—), an amide group (—CONH—), or a phenylene group. Among these, when L 11 is an amide group, the polymerizability and solvent resistance (for example, alkali solvent resistance) of the obtained layer to be plated are improved.
L 12 represents a single bond, a divalent aliphatic hydrocarbon group (preferably having 1 to 8 carbon atoms, more preferably 3 to 5 carbon atoms), or a divalent aromatic hydrocarbon group. The aliphatic hydrocarbon group may be linear, branched or cyclic. When L 12 is a single bond, L 11 represents a phenylene group.
 式(1)で表される化合物の分子量は特に制限されないが、揮発性、溶剤への溶解性、成膜性、および、取扱い性などの観点から、100~1000が好ましく、100~300がより好ましい。 The molecular weight of the compound represented by the formula (1) is not particularly limited, but is preferably from 100 to 1,000, more preferably from 100 to 300, from the viewpoints of volatility, solubility in a solvent, film formability, and handleability. preferable.
 被めっき層形成用組成物中の上記化合物の含有量は特に制限されないが、組成物全量に対して、2~50質量%が好ましく、5~30質量%がより好ましい。上記範囲内であれば、組成物の取扱い性に優れ、パターン状被めっき層の層厚の制御がしやすい。 The content of the above compound in the composition for forming a plated layer is not particularly limited, but is preferably 2 to 50% by mass, more preferably 5 to 30% by mass with respect to the total amount of the composition. If it is in the said range, the handleability of a composition is excellent and it is easy to control the layer thickness of a pattern-like to-be-plated layer.
 被めっき層形成用組成物には、取扱い性の点から、溶剤が含まれることが好ましい。
 使用できる溶剤は特に限定されず、例えば、水;メタノール、エタノール、プロパノール、エチレングリコール、1-メトキシ-2-プロパノール、グリセリン、プロピレングリコールモノメチルエーテルなどのアルコール系溶剤;酢酸などの酸;アセトン、メチルエチルケトン、シクロヘキサノンなどのケトン系溶剤;ホルムアミド、ジメチルアセトアミド、N-メチルピロリドンなどのアミド系溶剤;アセトニトリル、プロピオニトリルなどのニトリル系溶剤;酢酸メチル、酢酸エチルなどのエステル系溶剤;ジメチルカーボネート、ジエチルカーボネートなどのカーボネート系溶剤;この他にも、エーテル系溶剤、グリコール系溶剤、アミン系溶剤、チオール系溶剤、ハロゲン系溶剤などが挙げられる。
 このなかでも、アルコール系溶剤、アミド系溶剤、ケトン系溶剤、ニトリル系溶剤、カーボネート系溶剤が好ましい。
 被めっき層形成用組成物中の溶剤の含有量は特に制限されないが、組成物全量に対して、50~98質量%が好ましく、70~95質量%がより好ましい。上記範囲内であれば、組成物の取扱い性に優れ、パターン状被めっき層の層厚の制御などがしやすい。
The composition for forming a layer to be plated preferably contains a solvent from the viewpoint of handleability.
Solvents that can be used are not particularly limited. For example, water; alcohol solvents such as methanol, ethanol, propanol, ethylene glycol, 1-methoxy-2-propanol, glycerin, propylene glycol monomethyl ether; acids such as acetic acid; acetone, methyl ethyl ketone Ketone solvents such as cyclohexanone; amide solvents such as formamide, dimethylacetamide and N-methylpyrrolidone; nitrile solvents such as acetonitrile and propionitrile; ester solvents such as methyl acetate and ethyl acetate; dimethyl carbonate and diethyl carbonate Other examples include carbonate solvents such as ether solvents, glycol solvents, amine solvents, thiol solvents, and halogen solvents.
Of these, alcohol solvents, amide solvents, ketone solvents, nitrile solvents, and carbonate solvents are preferable.
The content of the solvent in the composition for forming a layer to be plated is not particularly limited, but is preferably 50 to 98% by mass, more preferably 70 to 95% by mass with respect to the total amount of the composition. If it is in the said range, the handleability of a composition is excellent and it is easy to control the layer thickness of a pattern-like to-be-plated layer.
 被めっき層形成用組成物には、重合開始剤が含まれていてもよい。重合開始剤が含まれることにより、化合物間、および、化合物と基板との間の結合がより形成され、結果として密着性により優れた引き出し配線を得ることができる。
 使用される重合開始剤としては特に制限はなく、例えば、熱重合開始剤、光重合開始剤などを用いることができる。光重合開始剤の例としては、ベンゾフェノン類、アセトフェノン類、α-アミノアルキルフェノン類、ベンゾイン類、ケトン類、チオキサントン類、ベンジル類、ベンジルケタール類、オキスムエステル類、アンソロン類、テトラメチルチウラムモノサルファイド類、ビスアシルフォスフィノキサイド類、アシルフォスフィンオキサイド類、アントラキノン類、アゾ化合物等およびその誘導体を挙げることができる。
 また、熱重合開始剤の例としては、ジアゾ系化合物、または、ペルオキサイド系化合物などが挙げられる。
 被めっき層形成用組成物中に重合開始剤が含まれる場合、重合開始剤の含有量は組成物全量に対して、0.01~1質量%であることが好ましく、0.1~0.5質量%であることがより好ましい。上記範囲内であれば、組成物の取扱い性に優れ、得られる引き出し配線の密着性がより優れる。
A polymerization initiator may be contained in the composition for forming a layer to be plated. By including the polymerization initiator, bonds between the compounds and between the compound and the substrate are further formed, and as a result, a lead-out wiring having better adhesion can be obtained.
There is no restriction | limiting in particular as a polymerization initiator used, For example, a thermal polymerization initiator, a photoinitiator, etc. can be used. Examples of photopolymerization initiators include benzophenones, acetophenones, α-aminoalkylphenones, benzoins, ketones, thioxanthones, benzyls, benzyl ketals, oxime esters, anthrones, tetramethylthiuram mono Mention may be made of sulfides, bisacylphosphine oxides, acylphosphine oxides, anthraquinones, azo compounds and the like and their derivatives.
Examples of the thermal polymerization initiator include a diazo compound or a peroxide compound.
When a polymerization initiator is contained in the composition for forming a layer to be plated, the content of the polymerization initiator is preferably 0.01 to 1% by mass with respect to the total amount of the composition, and preferably 0.1 to 0.001. More preferably, it is 5 mass%. If it is in the said range, it is excellent in the handleability of a composition and the adhesiveness of the extraction wiring obtained is more excellent.
 被めっき層形成用組成物には、モノマー(但し、上記式(X)または式(1)で表される化合物を除く)が含まれていてもよい。モノマーが含まれることにより、パターン状被めっき層中の架橋密度などを適宜制御することができる。
 使用されるモノマーは特に制限されず、例えば、付加重合性を有する化合物としてはエチレン性不飽和結合を有する化合物、開環重合性を有する化合物としてはエポキシ基を有する化合物等が挙げられる。なかでも、パターン状被めっき層中の架橋密度を向上し、引き出し配線の密着性がより向上する点から、多官能モノマーを使用することが好ましい。多官能モノマーとは、重合性基を2個以上有するモノマーを意味する。具体的には、2~6個の重合性基を有するモノマーを使用することが好ましい。
 反応性に影響を与える架橋反応中の分子の運動性の観点から、用いる多官能モノマーの分子量としては150~1000が好ましく、さらに好ましくは200~700である。また、複数存在する重合性基同士の間隔(距離)としては原子数で1~15であることが好ましく、6以上10以下であることがさらに好ましい。
The composition for forming a layer to be plated may contain a monomer (excluding the compound represented by the above formula (X) or formula (1)). By including the monomer, the crosslink density in the patterned layer to be plated can be appropriately controlled.
The monomer to be used is not particularly limited, and examples thereof include compounds having an ethylenically unsaturated bond as compounds having addition polymerizability, and compounds having an epoxy group as compounds having ring-opening polymerizability. Especially, it is preferable to use a polyfunctional monomer from the point which improves the crosslinking density in a pattern-like to-be-plated layer, and the adhesiveness of a lead-out wiring improves more. A polyfunctional monomer means a monomer having two or more polymerizable groups. Specifically, it is preferable to use a monomer having 2 to 6 polymerizable groups.
The molecular weight of the polyfunctional monomer used is preferably 150 to 1000, more preferably 200 to 700, from the viewpoint of molecular mobility during the crosslinking reaction that affects the reactivity. In addition, the interval (distance) between a plurality of polymerizable groups is preferably 1 to 15 atoms, and more preferably 6 or more and 10 or less.
 被めっき層形成用組成物には、他の添加剤(例えば、増感剤、硬化剤、重合禁止剤、酸化防止剤、帯電防止剤、紫外線吸収剤、フィラー、粒子、難燃剤、界面活性剤、滑剤、可塑剤など)を必要に応じて添加してもよい。 In the composition for forming a layer to be plated, other additives (for example, sensitizer, curing agent, polymerization inhibitor, antioxidant, antistatic agent, ultraviolet absorber, filler, particle, flame retardant, surfactant) , Lubricants, plasticizers, etc.) may be added as necessary.
 なお、上記では、相互作用性基および重合性基を有する化合物を含有する被めっき層形成用組成物について述べたが、この態様には限定されず、例えば、相互作用性基を有する化合物、および、重合性基を有する化合物を含む被めっき層形成用組成物であってもよい。
 相互作用性基および重合性基の定義は、上述の通りである。
 相互作用性基を有する化合物とは、相互作用性基を有する化合物である。相互作用性基の定義は上述の通りである。このような化合物としては、低分子化合物であっても、高分子化合物であってもよい。相互作用性基を有する化合物の好適態様としては、上述した式(b)で表される繰り返し単位を有する高分子(例えば、ポリアクリル酸)が挙げられる。なお、相互作用性基を有する化合物には、重合性基は含まれない。
 重合性基を有する化合物とは、いわゆるモノマーであり、形成される被めっき層の硬度がより優れる点で、2個以上の重合性基を有する多官能モノマーであることが好ましい。多官能モノマーとは、具体的には、2~6個の重合性基を有するモノマーを使用することが好ましい。反応性に影響を与える架橋反応中の分子の運動性の観点から、用いる多官能モノマーの分子量としては150~1000が好ましく、さらに好ましくは200~700である。また、複数存在する重合性基同士の間隔(距離)としては原子数で1~15であることが好ましく、6~10であることがより好ましい。
In the above description, the composition for forming a plating layer containing a compound having an interactive group and a polymerizable group has been described. However, the present invention is not limited to this embodiment. A composition for forming a layer to be plated containing a compound having a polymerizable group may also be used.
The definitions of the interactive group and the polymerizable group are as described above.
The compound having an interactive group is a compound having an interactive group. The definition of the interactive group is as described above. Such a compound may be a low molecular compound or a high molecular compound. As a suitable aspect of the compound which has an interactive group, the polymer (for example, polyacrylic acid) which has a repeating unit represented by the formula (b) mentioned above is mentioned. The compound having an interactive group does not contain a polymerizable group.
The compound having a polymerizable group is a so-called monomer, and is preferably a polyfunctional monomer having two or more polymerizable groups in that the formed layer to be plated is more excellent in hardness. Specifically, it is preferable to use a monomer having 2 to 6 polymerizable groups as the polyfunctional monomer. The molecular weight of the polyfunctional monomer used is preferably 150 to 1000, more preferably 200 to 700, from the viewpoint of molecular mobility during the crosslinking reaction that affects the reactivity. In addition, the distance (distance) between a plurality of polymerizable groups is preferably 1 to 15 and more preferably 6 to 10 in terms of the number of atoms.
(工程1の手順)
 工程1では、まず、基板上に被めっき層形成用組成物を配置するが、その方法は特に制限されず、例えば、上記被めっき層形成用組成物を基板上に接触させて、被めっき層形成用組成物の塗膜(被めっき層前駆体層)を形成する方法が挙げられる。この方法としては、例えば、上記被めっき層形成用組成物を基板上に塗布する方法(塗布法)が挙げられる。
 塗布法の場合に、被めっき層形成用組成物を基板上に塗布する方法は特に制限されず、公知の方法(例えば、スピンコート、ダイコート、ディップコートなど)を使用できる。
 取り扱い性や製造効率の観点からは、被めっき層形成用組成物を基板上に塗布し、必要に応じて乾燥処理を行って残存する溶剤を除去して、塗膜を形成する態様が好ましい。
 なお、乾燥処理の条件は特に制限されないが、生産性がより優れる点で、室温~220℃(好ましくは50~120℃)で、1~30分間(好ましく1~10分間)実施することが好ましい。
(Procedure of step 1)
In step 1, the composition for forming a layer to be plated is first disposed on the substrate, but the method is not particularly limited. For example, the composition for forming a layer to be plated is brought into contact with the substrate to form a layer to be plated. The method of forming the coating film (to-be-plated layer precursor layer) of the composition for formation is mentioned. Examples of this method include a method (coating method) in which the composition for forming a layer to be plated is applied onto a substrate.
In the coating method, the method for coating the composition for forming a layer to be plated on the substrate is not particularly limited, and a known method (for example, spin coating, die coating, dip coating, etc.) can be used.
From the viewpoint of handleability and production efficiency, an embodiment in which a composition for forming a layer to be plated is applied on a substrate and, if necessary, a drying treatment is performed to remove the remaining solvent to form a coating film.
The conditions for the drying treatment are not particularly limited, but are preferably carried out at room temperature to 220 ° C. (preferably 50 to 120 ° C.) for 1 to 30 minutes (preferably 1 to 10 minutes) from the viewpoint of better productivity. .
 基板上の上記化合物を含む塗膜にパターン状にエネルギー付与する方法は特に制限されない。例えば、加熱処理や露光処理(光照射処理)などが用いられることが好ましく、処理が短時間で終わる点より、露光処理が好ましい。塗膜にエネルギーを付与することにより、化合物中の重合性基が活性化され、化合物間の架橋が生じ、層の硬化が進行する。
 露光処理には、UV(紫外光)ランプ、可視光線などによる光照射等が用いられる。光源としては、例えば、水銀灯、メタルハライドランプ、キセノンランプ、ケミカルランプ、カーボンアーク灯、等がある。放射線としては、電子線、X線、イオンビーム、遠赤外線などもある。具体的な態様としては、赤外線レーザによる走査露光、キセノン放電灯などの高照度フラッシュ露光や、赤外線ランプ露光などが好適に挙げられる。
 露光時間としては、化合物の反応性および光源により異なるが、通常、10秒~5時間の間である。露光エネルギーとしては、10~8000mJ程度であればよく、好ましくは50~3000mJの範囲である。
 なお、上記露光処理をパターン状に実施する方法は特に制限されず、公知の方法が採用され、例えば、マスクを介して露光光を塗膜に照射すればよい。
The method for applying energy in a pattern to the coating film containing the compound on the substrate is not particularly limited. For example, it is preferable to use a heat treatment or an exposure process (light irradiation process), and the exposure process is preferable because the process is completed in a short time. By imparting energy to the coating film, the polymerizable group in the compound is activated, crosslinking between the compounds occurs, and the curing of the layer proceeds.
For the exposure process, UV (ultraviolet light) lamp, light irradiation with visible light, or the like is used. Examples of the light source include a mercury lamp, a metal halide lamp, a xenon lamp, a chemical lamp, and a carbon arc lamp. Examples of radiation include electron beams, X-rays, ion beams, and far infrared rays. Specific examples of preferred embodiments include scanning exposure with an infrared laser, high-illuminance flash exposure such as a xenon discharge lamp, and infrared lamp exposure.
The exposure time varies depending on the reactivity of the compound and the light source, but is usually between 10 seconds and 5 hours. The exposure energy may be about 10 to 8000 mJ, preferably 50 to 3000 mJ.
In addition, the method in particular which implements the said exposure process in a pattern form is not restrict | limited, A well-known method is employ | adopted, for example, what is necessary is just to irradiate a coating film with exposure light through a mask.
 また、エネルギー付与として加熱処理を用いる場合、送風乾燥機、オーブン、赤外線乾燥機、加熱ドラムなどを用いることができる。 In addition, when heat treatment is used for energy application, an air dryer, an oven, an infrared dryer, a heating drum, or the like can be used.
 次に、塗膜中のエネルギー付与が実施されなかった部分を除去して、パターン状被めっき層を形成する。
 上記除去方法は特に制限されず、使用される化合物によって適宜最適な方法が選択される。例えば、アルカリ性溶液(好ましくはpH:13.0~13.8)を現像液として用いる方法が挙げられる。アルカリ性溶液を用いて、エネルギー未付与領域を除去する場合は、エネルギーが付与された塗膜を有する基板を溶液中に浸漬させる方法や、その基板上に現像液を塗布する方法などが挙げられるが、浸漬する方法が好ましい。浸漬する方法の場合、浸漬時間としては生産性・作業性などの観点から、1分から30分程度が好ましい。
 また、他の方法としては、上記化合物が溶解する溶剤を現像液とし、それに浸漬する方法が挙げられる。
Next, the portion of the coating film where energy is not applied is removed to form a patterned layer to be plated.
The removal method is not particularly limited, and an optimal method is appropriately selected depending on the compound used. For example, a method using an alkaline solution (preferably pH: 13.0 to 13.8) as a developing solution can be mentioned. In the case of removing an energy non-applied region using an alkaline solution, there are a method of immersing a substrate having a coating film to which energy is applied in a solution, a method of applying a developer on the substrate, and the like. The soaking method is preferred. In the case of the dipping method, the dipping time is preferably about 1 to 30 minutes from the viewpoint of productivity and workability.
In addition, as another method, a method in which a solvent in which the above compound is dissolved is used as a developing solution and immersed in the developing solution.
[工程2:引き出し配線形成工程]
 工程2は、上記工程1で形成されたパターン状被めっき層にめっき触媒またはその前駆体を付与して、めっき触媒またはその前駆体が付与されたパターン状被めっき層に対してめっき処理を行い、パターン状被めっき層上に引き出し配線を形成する工程である。図4(D)に示すように、本工程を実施することにより、パターン状被めっき層16上に引き出し配線18が配置される。
 以下では、パターン状被めっき層にめっき触媒またはその前駆体を付与する工程(工程2-1)と、めっき触媒またはその前駆体が付与されたパターン状被めっき層に対してめっき処理を行う工程(工程2-2)とに分けて説明する。
[Step 2: Lead-out wiring formation step]
Step 2 applies a plating catalyst or a precursor thereof to the patterned plating layer formed in Step 1 above, and performs a plating process on the patterned plating layer provided with the plating catalyst or the precursor thereof. This is a step of forming a lead-out wiring on the patterned layer to be plated. As shown in FIG. 4D, by carrying out this step, the lead-out wiring 18 is arranged on the patterned layer 16 to be plated.
In the following, a step of applying a plating catalyst or a precursor thereof to the patterned layer to be plated (step 2-1), and a step of performing a plating process on the patterned layer of plating to which the plating catalyst or its precursor has been applied This will be described separately in (Step 2-2).
(工程2-1:めっき触媒付与工程)
 本工程では、まず、パターン状被めっき層にめっき触媒またはその前駆体を付与する。上記化合物由来の相互作用性基が、その機能に応じて、付与されためっき触媒またはその前駆体を付着(吸着)する。より具体的には、被めっき層中および被めっき層表面上に、めっき触媒またはその前駆体が付与される。
 めっき触媒またはその前駆体は、めっき処理の触媒や電極として機能するものである。そのため、使用されるめっき触媒またはその前駆体の種類は、めっき処理の種類により適宜決定される。
 なお、用いられるめっき触媒またはその前駆体は、無電解めっき触媒またはその前駆体であることが好ましい。以下で、主に、無電解めっき触媒またはその前駆体などについて詳述する。
(Step 2-1: Plating catalyst application step)
In this step, first, a plating catalyst or a precursor thereof is applied to the patterned layer to be plated. The interactive group derived from the compound adheres (adsorbs) the applied plating catalyst or its precursor depending on its function. More specifically, a plating catalyst or a precursor thereof is applied in the layer to be plated and on the surface of the layer to be plated.
The plating catalyst or a precursor thereof functions as a catalyst or an electrode for plating treatment. Therefore, the type of plating catalyst or precursor used is appropriately determined depending on the type of plating treatment.
In addition, it is preferable that the plating catalyst used or its precursor is an electroless plating catalyst or its precursor. Hereinafter, mainly the electroless plating catalyst or its precursor will be described in detail.
 本工程において用いられる無電解めっき触媒は、無電解めっき時の活性核となるものであれば、如何なるものも用いることができ、具体的には、自己触媒還元反応の触媒能を有する金属(Niよりイオン化傾向の低い無電解めっきできる金属として知られるもの)などが挙げられる。具体的には、Pd、Ag、Cu、Ni、Pt、Au、Coなどが挙げられる。なかでも、触媒能の高さから、Ag、Pd、Pt、Cuが特に好ましい。
 この無電解めっき触媒としては、金属コロイドを用いてもよい。
 本工程において用いられる無電解めっき触媒前駆体とは、化学反応により無電解めっき触媒となりうるものであれば、特に制限なく使用することができる。主には、上記無電解めっき触媒として挙げた金属の金属イオンが用いられる。無電解めっき触媒前駆体である金属イオンは、還元反応により無電解めっき触媒である0価金属になる。無電解めっき触媒前駆体である金属イオンはパターン状被めっき層へ付与された後、無電解めっき浴への浸漬前に、別途還元反応により0価金属に変化させて無電解めっき触媒としてもよい。また、無電解めっき触媒前駆体のまま無電解めっき浴に浸漬し、無電解めっき浴中の還元剤により金属(無電解めっき触媒)に変化させてもよい。
As the electroless plating catalyst used in this step, any catalyst can be used as long as it becomes an active nucleus at the time of electroless plating. Specifically, a metal (Ni) having catalytic ability for autocatalytic reduction reaction. And those known as metals capable of electroless plating with a lower ionization tendency). Specific examples include Pd, Ag, Cu, Ni, Pt, Au, and Co. Of these, Ag, Pd, Pt, and Cu are particularly preferable because of their high catalytic ability.
A metal colloid may be used as the electroless plating catalyst.
The electroless plating catalyst precursor used in this step can be used without particular limitation as long as it can become an electroless plating catalyst by a chemical reaction. The metal ions of the metals mentioned as the electroless plating catalyst are mainly used. The metal ion that is an electroless plating catalyst precursor becomes a zero-valent metal that is an electroless plating catalyst by a reduction reaction. After the metal ion that is the electroless plating catalyst precursor is applied to the patterned layer to be plated, and before being immersed in the electroless plating bath, it may be changed to a zero-valent metal by a reduction reaction separately to be used as an electroless plating catalyst. . Alternatively, the electroless plating catalyst precursor may be immersed in an electroless plating bath and changed to a metal (electroless plating catalyst) by a reducing agent in the electroless plating bath.
 無電解めっき触媒前駆体である金属イオンは、金属塩を用いてパターン状被めっき層16に付与することが好ましい。使用される金属塩としては、適切な溶媒に溶解して金属イオンと塩基(陰イオン)とに解離されるものであれば特に制限はなく、M(NO3)n、MCln、M2/n(SO4)、M3/n(PO4)(Mは、n価の金属原子を表す)などが挙げられる。金属イオンとしては、上記の金属塩が解離したものを好適に用いることができる。例えば、Agイオン、Cuイオン、Niイオン、Coイオン、Ptイオン、Pdイオンが挙げられる。なかでも、多座配位可能なものが好ましく、特に、配位可能な官能基の種類数および触媒能の点で、Agイオン、Pdイオン、Cuイオンが好ましい。
 本工程において、無電解めっきを行わず直接電気めっきを行うために用いられる触媒として、0価金属を使用することもできる。
It is preferable that the metal ion which is an electroless plating catalyst precursor is provided to the patterned layer 16 by using a metal salt. The metal salt used is not particularly limited as long as it is dissolved in a suitable solvent and dissociated into a metal ion and a base (anion), and M (NO 3 ) n , MCl n , M 2 / n (SO 4 ), M 3 / n (PO 4 ) (M represents an n-valent metal atom), and the like. As a metal ion, the thing which said metal salt dissociated can be used suitably. For example, Ag ion, Cu ion, Ni ion, Co ion, Pt ion, Pd ion can be mentioned. Among them, those capable of multidentate coordination are preferable, and Ag ions, Pd ions, and Cu ions are particularly preferable in terms of the number of types of functional groups capable of coordination and catalytic ability.
In this step, a zero-valent metal can also be used as a catalyst used for direct electroplating without electroless plating.
 めっき触媒またはその前駆体をパターン状被めっき層16に付与する方法としては、例えば、めっき触媒またはその前駆体を適切な溶剤に分散または溶解させた溶液(めっき触媒液)を調製し、その溶液をパターン状被めっき層上に塗布するか、または、その溶液中にパターン状被めっき層が形成された基板を浸漬すればよい。
 上記溶剤としては、水や有機溶剤が適宜使用される。有機溶剤としては、パターン状被めっき層に浸透しうる溶剤が好ましく、例えば、アセトン、アセト酢酸メチル、アセト酢酸エチル、エチレングリコールジアセテート、シクロヘキサノン、アセチルアセトン、アセトフェノン、2-(1-シクロヘキセニル)シクロヘキサノン、プロピレングリコールジアセテート、トリアセチン、ジエチレングリコールジアセテート、ジオキサン、N-メチルピロリドン、ジメチルカーボネート、ジメチルセロソルブなどを用いることができる。
As a method for applying the plating catalyst or a precursor thereof to the patterned layer 16, for example, a solution (plating catalyst solution) in which the plating catalyst or the precursor thereof is dispersed or dissolved in an appropriate solvent is prepared, and the solution May be applied on the patterned layer to be plated, or a substrate on which the patterned layer to be plated is immersed in the solution.
As said solvent, water and an organic solvent are used suitably. The organic solvent is preferably a solvent that can penetrate the patterned layer to be plated, for example, acetone, methyl acetoacetate, ethyl acetoacetate, ethylene glycol diacetate, cyclohexanone, acetylacetone, acetophenone, 2- (1-cyclohexenyl) cyclohexanone. Propylene glycol diacetate, triacetin, diethylene glycol diacetate, dioxane, N-methylpyrrolidone, dimethyl carbonate, dimethyl cellosolve and the like can be used.
 めっき触媒またはその前駆体、および、溶剤を含む触媒付与液のpHは特に制限されないが、後述するめっき処理の際に、所望の位置に所望の量の金属層が形成されやすい点で、3.0~7.0であることが好ましく、3.2~6.8がより好ましく、3.5~6.6がさらに好ましい。
 触媒付与液の調製方法は特に制限されず、所定の金属塩を適切な溶剤で溶解させ、必要に応じて、酸またはアルカリを用いてpHを所定の範囲に調整する。
The pH of the catalyst-providing liquid containing the plating catalyst or its precursor and the solvent is not particularly limited. It is preferably 0 to 7.0, more preferably 3.2 to 6.8, and even more preferably 3.5 to 6.6.
The method for preparing the catalyst-imparting solution is not particularly limited, and a predetermined metal salt is dissolved in an appropriate solvent, and the pH is adjusted to a predetermined range using an acid or an alkali as necessary.
 溶液中のめっき触媒またはその前駆体の濃度は特に制限されないが、0.001~50質量%であることが好ましく、0.005~30質量%であることがより好ましい。
 また、接触時間としては、30秒~24時間程度であることが好ましく、1分~1時間程度であることがより好ましい。
The concentration of the plating catalyst or its precursor in the solution is not particularly limited, but is preferably 0.001 to 50% by mass, and more preferably 0.005 to 30% by mass.
The contact time is preferably about 30 seconds to 24 hours, more preferably about 1 minute to 1 hour.
 パターン状被めっき層16のめっき触媒またはその前駆体の吸着量に関しては、使用するめっき浴種、触媒金属種、パターン状被めっき層16の相互作用性基種、使用方法等により異なるが、めっきの析出性の観点から、5~1000mg/m2が好ましく、10~800mg/m2がより好ましく、特に20~600mg/m2が好ましい。 The amount of adsorption of the plating catalyst or precursor of the patterned layer 16 varies depending on the type of plating bath used, the type of catalytic metal, the type of interactive base of the patterned layer 16 to be used, the method of use, etc. from the viewpoint of deposition properties, preferably 5 ~ 1000mg / m 2, more preferably 10 ~ 800mg / m 2, particularly preferably 20 ~ 600mg / m 2.
(工程2-2:めっき処理工程)
 次に、めっき触媒またはその前駆体が付与されたパターン状被めっき層に対してめっき処理を行う。
 めっき処理の方法は特に制限されず、例えば、無電解めっき処理、または、電解めっき処理(電気めっき処理)が挙げられる。本工程では、無電解めっき処理を単独で実施してもよいし、無電解めっき処理を実施した後にさらに電解めっき処理を実施してもよい。
 なお、本明細書においては、いわゆる銀鏡反応は、上記無電解めっき処理の一種として含まれる。よって、例えば、銀鏡反応などによって、付着させた金属イオンを還元させて、所望のパターン状金属層を形成してもよく、さらにその後電解めっき処理を実施してもよい。
 以下、無電解めっき処理、および、電解めっき処理の手順について詳述する。
(Process 2-2: Plating process)
Next, a plating treatment is performed on the patterned layer to which the plating catalyst or its precursor is applied.
The method for the plating treatment is not particularly limited, and examples thereof include electroless plating treatment or electrolytic plating treatment (electroplating treatment). In this step, the electroless plating process may be performed alone, or after the electroless plating process, the electrolytic plating process may be further performed.
In the present specification, so-called silver mirror reaction is included as a kind of the electroless plating process. Therefore, for example, the deposited metal ions may be reduced by a silver mirror reaction or the like to form a desired patterned metal layer, and then an electrolytic plating process may be performed.
Hereinafter, the procedures of the electroless plating process and the electrolytic plating process will be described in detail.
 無電解めっき処理とは、めっきとして析出させたい金属イオンを溶かした溶液を用いて、化学反応によって金属を析出させる操作のことをいう。
 本工程における無電解めっきは、例えば、無電解めっき触媒が付与されたパターン状被めっき層を備える基板を、水洗して余分な無電解めっき触媒(金属)を除去した後、無電解めっき浴に浸漬して行うことが好ましい。使用される無電解めっき浴としては、公知の無電解めっき浴を使用することができる。
 また、無電解めっき触媒前駆体が付与されたパターン状被めっき層を備える基板を、無電解めっき触媒前駆体がパターン状被めっき層に吸着または含浸した状態で無電解めっき浴に浸漬する場合には、基板を水洗して余分な無電解めっき触媒前駆体(金属塩など)を除去した後、無電解めっき浴中へ浸漬させることが好ましい。この場合には、無電解めっき浴中において、無電解めっき触媒前駆体の還元とこれに引き続き無電解めっきが行われる。ここで使用される無電解めっき浴としても、上記同様、公知の無電解めっき浴を使用することができる。
 尚、無電解めっき触媒前駆体の還元は、上記のような無電解めっき液を用いる態様とは別に、触媒活性化液(還元液)を準備し、無電解めっき前の別工程として行うことも可能である。
The electroless plating treatment refers to an operation of depositing a metal by a chemical reaction using a solution in which metal ions to be deposited as a plating are dissolved.
In the electroless plating in this step, for example, a substrate provided with a pattern-like plated layer provided with an electroless plating catalyst is washed with water to remove excess electroless plating catalyst (metal), and then the electroless plating bath is used. It is preferable to immerse. As the electroless plating bath used, a known electroless plating bath can be used.
In addition, when a substrate provided with a patterned plating layer provided with an electroless plating catalyst precursor is immersed in an electroless plating bath in a state where the electroless plating catalyst precursor is adsorbed or impregnated in the patterned plating layer Preferably, the substrate is washed with water to remove excess electroless plating catalyst precursor (such as a metal salt) and then immersed in an electroless plating bath. In this case, reduction of the electroless plating catalyst precursor and subsequent electroless plating are performed in the electroless plating bath. As the electroless plating bath used here, a known electroless plating bath can be used as described above.
In addition, the reduction of the electroless plating catalyst precursor may be performed as a separate process before electroless plating by preparing a catalyst activation liquid (reducing liquid) separately from the embodiment using the electroless plating liquid as described above. Is possible.
 一般的な無電解めっき浴の組成としては、溶剤(例えば、水)の他に、1.めっき用の金属イオン、2.還元剤、3.金属イオンの安定性を向上させる添加剤(安定剤)が主に含まれている。このめっき浴には、これらに加えて、めっき浴の安定剤など公知の添加剤が含まれていてもよい。
 無電解めっき浴に用いられる有機溶剤としては、水に可能な溶剤であることが好ましく、その点から、アセトンなどのケトン類、メタノール、エタノール、イソプロパノールなどのアルコール類が好ましく用いられる。無電解めっき浴に用いられる金属の種類としては、銅、すず、鉛、ニッケル、金、銀、パラジウム、ロジウムが知られており、なかでも、導電性の観点からは、銅、銀、金が好ましく、銅がより好ましい。また、上記金属に合わせて最適な還元剤、添加剤が選択される。
 無電解めっき浴への浸漬時間としては、1分~6時間程度であることが好ましく、1分~3時間程度であることがより好ましい。
As a composition of a general electroless plating bath, in addition to a solvent (for example, water), 1. 1. metal ions for plating; 2. reducing agent; Additives (stabilizers) that improve the stability of metal ions are mainly included. In addition to these, the plating bath may contain known additives such as a plating bath stabilizer.
The organic solvent used in the electroless plating bath is preferably a solvent that can be used with water, and from this point, ketones such as acetone and alcohols such as methanol, ethanol, and isopropanol are preferably used. Copper, tin, lead, nickel, gold, silver, palladium, and rhodium are known as the types of metals used in the electroless plating bath. Among these, copper, silver, and gold are preferable from the viewpoint of conductivity. Preferably, copper is more preferable. Moreover, the optimal reducing agent and additive are selected according to the said metal.
The immersion time in the electroless plating bath is preferably about 1 minute to 6 hours, and more preferably about 1 minute to 3 hours.
 本工程おいては、パターン状被めっき層に付与されためっき触媒またはその前駆体が電極としての機能を有する場合、その触媒またはその前駆体が付与されたパターン状被めっき層に対して、電気めっきを行うことができる。
 なお、上述したように、本工程においては、上記無電解めっき処理の後に、必要に応じて、電解めっき処理を行うことができる。このような態様では、形成される引き出し配線の厚みを適宜調整可能である。
 電気めっきの方法としては、従来公知の方法を用いることができる。尚、電気めっきに用いられる金属としては、銅、クロム、鉛、ニッケル、金、銀、すず、亜鉛などが挙げられ、導電性の観点から、銅、金、銀が好ましく、銅がより好ましい。
In this step, when the plating catalyst or its precursor applied to the patterned layer to be plated has a function as an electrode, the electroplating layer to which the catalyst or its precursor is applied Plating can be performed.
In addition, as above-mentioned, in this process, an electroplating process can be performed as needed after the said electroless-plating process. In such an aspect, the thickness of the formed lead wiring can be adjusted as appropriate.
As a method of electroplating, a conventionally known method can be used. In addition, as a metal used for electroplating, copper, chromium, lead, nickel, gold | metal | money, silver, tin, zinc etc. are mentioned, Copper, gold | metal | money, silver is preferable from a conductive viewpoint, and copper is more preferable.
[導電性接続部]
 導電性接続部24は、検出電極14と引き出し配線18とを電気的に接続する接続部である。導電性接続部24は、検出電極14および引き出し配線18それぞれと接するように配置される。導電性接続部24が配置されることにより、検出電極14と引き出し配線18との導通性がより向上する。
 導電性接続部24を構成する材料は特に制限されず、導電性を示す材料であればよく、例えば、金(Au)、銀(Ag)、銅(Cu)、アルミニウム(Al)などの金属(合金を含む)や、導電性樹脂などが挙げられる。なお、金属としては、金属微粒子の形態が挙げられる。
 導電性接続部24の形成方法は特に制限されないが、導電性組成物(いわゆる、導電性ペーストまたは導電性インク)を用いる態様が好ましい。つまり、導電性接続部24は、導電性組成物より形成された接続部であることが好ましい。具体的には、導電性組成物をインクジェット法、スクリーン印刷法、フレキソ印刷法、グラビア印刷法などの印刷法によって、検出電極14および引き出し配線18に接するように塗布して、必要に応じて、硬化処理を施すことにより形成される。
 なお、導電性ペーストと導電性インクとの差は、分散媒にともなう粘度の違いであり、導電性ペーストでは、一般的に分散媒として高分子成分が含まれるため粘度が高く、スクリーン印刷法やフレキソ印刷法などが好適に利用できる。導電性インクでは、一般的に分散媒として低分子成分が含まれるため粘度が低く、インクジェット法などが好適に利用できる。
[Conductive connection]
The conductive connection portion 24 is a connection portion that electrically connects the detection electrode 14 and the lead wiring 18. The conductive connection portion 24 is disposed so as to be in contact with the detection electrode 14 and the extraction wiring 18. By disposing the conductive connection portion 24, the conductivity between the detection electrode 14 and the lead-out wiring 18 is further improved.
The material constituting the conductive connection portion 24 is not particularly limited as long as it is a material exhibiting conductivity. For example, a metal such as gold (Au), silver (Ag), copper (Cu), aluminum (Al) ( Alloy) and conductive resins. In addition, as a metal, the form of metal fine particles is mentioned.
The method for forming the conductive connection portion 24 is not particularly limited, but an embodiment using a conductive composition (so-called conductive paste or conductive ink) is preferable. That is, it is preferable that the electroconductive connection part 24 is a connection part formed from the electroconductive composition. Specifically, the conductive composition is applied so as to be in contact with the detection electrode 14 and the lead-out wiring 18 by a printing method such as an inkjet method, a screen printing method, a flexographic printing method, or a gravure printing method, and if necessary, It is formed by performing a curing process.
The difference between the conductive paste and the conductive ink is a difference in viscosity due to the dispersion medium, and the conductive paste generally has a high viscosity because it contains a polymer component as a dispersion medium. A flexographic printing method can be suitably used. In the conductive ink, a low molecular component is generally contained as a dispersion medium, so that the viscosity is low, and an ink jet method or the like can be suitably used.
[基板]
 基板12は、2つの主面を有し、中央領域EIにおいて検出電極14を支持すると共に、外側領域EOにおいてパターン状被めっき層16を支持する役割を担う部材である。
 基板12の種類は特に制限されず、例えば、絶縁基板が挙げられ、より具体的には、樹脂基板、セラミック基板、ガラス基板などを使用することができる。
 樹脂基板の材料としては、例えば、ポリエチレンテレフタレート、ポリエチレンナフタレート、ポリエーテルスルホン、ポリアクリル系樹脂、ポリウレタン系樹脂、ポリエステル、ポリカーボネート、ポリスルホン、ポリアミド、ポリアリレート、ポリオレフィン、セルロース系樹脂、ポリ塩化ビニル、シクロオレフィン系樹脂などが挙げられる。なかでも、ポリエチレンテレフタレート、ポリエチレンナフタレート、または、ポリオレフィンが好ましい。
 基板12の厚み(mm)は特に制限されないが、取り扱い性および薄型化のバランスの点から、0.05~2mmが好ましく、0.1~1mmがより好ましい。
 また、基板12は、光を適切に透過することが好ましい。具体的には、基板12の全光線透過率は、85~100%であることが好ましい。
[substrate]
The substrate 12 has two main surfaces and is a member that supports the detection electrode 14 in the central region E I and supports the patterned plated layer 16 in the outer region E O.
The kind in particular of board | substrate 12 is not restrict | limited, For example, an insulating substrate is mentioned, More specifically, a resin substrate, a ceramic substrate, a glass substrate etc. can be used.
Examples of the resin substrate material include polyethylene terephthalate, polyethylene naphthalate, polyethersulfone, polyacrylic resin, polyurethane resin, polyester, polycarbonate, polysulfone, polyamide, polyarylate, polyolefin, cellulose resin, polyvinyl chloride, Examples thereof include cycloolefin resins. Of these, polyethylene terephthalate, polyethylene naphthalate, or polyolefin is preferable.
The thickness (mm) of the substrate 12 is not particularly limited, but is preferably 0.05 to 2 mm, more preferably 0.1 to 1 mm, from the viewpoint of the balance between handleability and thinning.
Moreover, it is preferable that the board | substrate 12 permeate | transmits light appropriately. Specifically, the total light transmittance of the substrate 12 is preferably 85 to 100%.
(プライマー層(密着補助層))
 基板とパターン状被めっき層(または、被めっき層)との密着性は、基板の表面状態や剛性により影響を受ける場合もある。そのために、基板の種類に応じて適宜、基板とパターン状被めっき層(または、被めっき層)との密着性を高めるためのプライマー層を基板上に配置してもよい。言い換えると、基板とパターン状被めっき層(または、被めっき層)との間にプライマー層を介在させてもよい。
 プライマー層によってパターン状被めっき層(または、被めっき層)の密着性を高めるためには、表面エネルギーを制御すること、被めっき層との化学結合を形成すること、または、応力緩和による粘着力を利用する等、種々の密着力向上の手段を取ることができる。表面エネルギー制御の場合、例えば、被めっき層の表面エネルギーに近い低分子層や高分子層を用いることができる。化学結合を形成する場合は、重合活性部位を有する低分子層や高分子層を用いることができる。応力緩和による粘着力を利用する場合は、弾性率の低いゴム性の樹脂等を用いることができる。
(Primer layer (adhesion auxiliary layer))
The adhesion between the substrate and the patterned plating layer (or plating layer) may be affected by the surface state and rigidity of the substrate. Therefore, a primer layer for improving the adhesion between the substrate and the pattern-like plated layer (or the plated layer) may be appropriately disposed on the substrate depending on the type of the substrate. In other words, a primer layer may be interposed between the substrate and the pattern-like plated layer (or plated layer).
In order to improve the adhesion of the patterned layer to be plated (or the layer to be plated) with the primer layer, the surface energy is controlled, the chemical bond with the layer to be plated is formed, or the adhesive force by stress relaxation It is possible to take various measures for improving the adhesion, such as using In the case of surface energy control, for example, a low molecular layer or a polymer layer close to the surface energy of the layer to be plated can be used. In the case of forming a chemical bond, a low molecular layer or a high molecular layer having a polymerization active site can be used. In the case where the adhesive force due to stress relaxation is used, a rubber-like resin having a low elastic modulus can be used.
 プライマー層の厚みは特に制限されないが、一般的には、0.01~100μmが好ましく、0.05~20μmがより好ましく、0.05~10μmがさらに好ましい。
 プライマー層の材料は特に制限されず、基板との密着性が良好な樹脂であることが好ましい。樹脂の具体例としては、例えば、熱硬化性樹脂でも熱可塑性樹脂でもまたそれらの混合物でもよく、例えば、熱硬化性樹脂としては、エポキシ樹脂、フェノール樹脂、ポリイミド樹脂、ポリエステル樹脂、ビスマレイミド樹脂、ポリオレフィン系樹脂、イソシアネート系樹脂等が挙げられる。熱可塑性樹脂としては、例えば、フェノキシ樹脂、ポリエーテルスルフォン、ポリスルフォン、ポリフェニレンスルフォン、ポリフェニレンサルファイド、ポリフェニルエーテル、ポリエーテルイミド、ABS樹脂等が挙げられる。
 熱可塑性樹脂と熱硬化性樹脂とは、それぞれ単独で用いてもよいし、2種以上併用してもよい。また、シアノ基を含有する樹脂を使用してもよく、具体的には、ABS樹脂や、特開2010-84196号〔0039〕~〔0063〕記載の「側鎖にシアノ基を有するユニットを含むポリマー」を用いてもよい。
 また、NBRゴム(アクリロニトリル・ブタジエンゴム)やSBRゴム(スチレン・ブタジエンゴム)などのゴム成分を用いることもできる。
The thickness of the primer layer is not particularly limited, but is generally preferably 0.01 to 100 μm, more preferably 0.05 to 20 μm, and further preferably 0.05 to 10 μm.
The material for the primer layer is not particularly limited, and is preferably a resin having good adhesion to the substrate. Specific examples of the resin may be, for example, a thermosetting resin, a thermoplastic resin, or a mixture thereof. For example, as the thermosetting resin, an epoxy resin, a phenol resin, a polyimide resin, a polyester resin, a bismaleimide resin, Examples include polyolefin resins and isocyanate resins. Examples of the thermoplastic resin include phenoxy resin, polyether sulfone, polysulfone, polyphenylene sulfone, polyphenylene sulfide, polyphenyl ether, polyether imide, and ABS resin.
The thermoplastic resin and the thermosetting resin may be used alone or in combination of two or more. In addition, a resin containing a cyano group may be used. Specifically, an ABS resin or “unit having a cyano group in the side chain” described in JP-A 2010-84196 [0039] to [0063] is included. "Polymer" may be used.
Also, rubber components such as NBR rubber (acrylonitrile / butadiene rubber) and SBR rubber (styrene / butadiene rubber) can be used.
 プライマー層を構成する材料の好適態様の一つとしては、水素添加されていてもよい共役ジエン化合物単位を有するポリマーが挙げられる。共役ジエン化合物単位とは、共役ジエン化合物由来の繰り返し単位を意味する。共役ジエン化合物としては、一つの単結合で隔てられた、二つの炭素-炭素二重結合を有する分子構造を有する化合物であれば特に制限されない。
 共役ジエン化合物由来の繰り返し単位の好適態様の一つとしては、ブタジエン骨格を有する化合物が重合反応することで生成する繰り返し単位が挙げられる。
 上記共役ジエン化合物単位は水素添加されていてもよく、水素添加された共役ジエン化合物単位を含む場合、パターン状金属層の密着性がより向上し好ましい。つまり、共役ジエン化合物由来の繰り返し単位中の二重結合が水素添加されていてもよい。
 水素添加されていてもよい共役ジエン化合物単位を有するポリマーには、上述した相互作用性基が含まれていてもよい。
 このポリマーの好適な態様としては、アクリロニトリルブタジエンゴム(NBR)、カルボキシル基含有ニトリルゴム(XNBR)、アクリロニトリル-ブタジエン-イソプレンゴム(NBIR)、アクリロニトリル-ブタジエン-スチレン共重合体(ABS樹脂)、または、これらの水素添加物(例えば、水素添加アクリロニトリルブタジエンゴム)などが挙げられる。
One preferred embodiment of the material constituting the primer layer includes a polymer having a conjugated diene compound unit that may be hydrogenated. The conjugated diene compound unit means a repeating unit derived from a conjugated diene compound. The conjugated diene compound is not particularly limited as long as it is a compound having a molecular structure having two carbon-carbon double bonds separated by one single bond.
One preferred embodiment of the repeating unit derived from a conjugated diene compound includes a repeating unit produced by a polymerization reaction of a compound having a butadiene skeleton.
The conjugated diene compound unit may be hydrogenated. When the conjugated diene compound unit includes a hydrogenated conjugated diene compound unit, the adhesion of the patterned metal layer is preferably improved. That is, the double bond in the repeating unit derived from the conjugated diene compound may be hydrogenated.
The above-mentioned interactive group may be contained in the polymer having a conjugated diene compound unit that may be hydrogenated.
Preferred examples of this polymer include acrylonitrile butadiene rubber (NBR), carboxyl group-containing nitrile rubber (XNBR), acrylonitrile-butadiene-isoprene rubber (NBIR), acrylonitrile-butadiene-styrene copolymer (ABS resin), or These hydrogenated products (for example, hydrogenated acrylonitrile butadiene rubber) and the like can be mentioned.
 プライマー層には、他の添加剤(例えば、増感剤、酸化防止剤、帯電防止剤、紫外線吸収剤、フィラー、粒子、難燃剤、界面活性剤、滑剤、可塑剤など)が含まれていてもよい。 The primer layer contains other additives (for example, sensitizers, antioxidants, antistatic agents, ultraviolet absorbers, fillers, particles, flame retardants, surfactants, lubricants, plasticizers, etc.). Also good.
 プライマー層の形成方法は特に制限されず、使用される樹脂を基板上にラミネートする方法や、必要な成分を溶解可能な溶剤に溶解し、塗布などの方法で基板表面上に塗布・乾燥する方法などが挙げられる。
 塗布方法における加熱温度と時間は、塗布溶剤が充分乾燥し得る条件を選択すればよいが、製造適性の点からは、加熱温度200℃以下、時間60分以内の範囲の加熱条件を選択することが好ましく、加熱温度40~100℃、時間20分以内の範囲の加熱条件を選択することがより好ましい。なお、使用される溶剤は、使用する樹脂に応じて適宜最適な溶剤(例えば、シクロヘキサノン、メチルエチルケトン)が選択される。
The method for forming the primer layer is not particularly limited, and a method of laminating a resin to be used on a substrate, a method in which a necessary component is dissolved in a soluble solvent, and a method such as coating and drying on a substrate surface Etc.
The heating temperature and time in the coating method may be selected so that the coating solvent can be sufficiently dried, but from the viewpoint of production suitability, the heating temperature should be 200 ° C. or less and the heating condition within the range of 60 minutes. It is preferable to select heating conditions in the range of heating temperature 40 to 100 ° C. and time 20 minutes or less. As the solvent to be used, an optimal solvent (for example, cyclohexanone or methyl ethyl ketone) is appropriately selected according to the resin to be used.
[検出電極]
 検出電極14は、本実施形態のタッチパネルセンサー用導電性フィルムが含まれるタッチパネルセンサー中において静電容量の変化を感知するセンシング電極であり、感知部(センシング部)を構成する。つまり、指先をタッチパネルに接触させると、検出電極14および他の電極との間の相互静電容量が変化し、この変化量に基づいて指先の位置をIC(integrated circuit)回路によって演算する。
 検出電極14は、中央領域EIに接近した操作者の指のX方向における入力位置の検出を行う役割を有するものであり、指との間に静電容量を発生する機能を有している。検出電極14は、第1方向(X方向)に延び、第1方向と直交する第2方向(Y方向)に所定の間隔をあけて配列された電極である。図1においては、検出電極14は5つ設けられているが、その数は特に制限されず複数あればよい。
 図1においては、検出電極14はベタ膜であるが、メッシュ状などの所定のパターンを含んでいてもよい。
[Detection electrode]
The detection electrode 14 is a sensing electrode that senses a change in capacitance in a touch panel sensor including the conductive film for a touch panel sensor of the present embodiment, and constitutes a sensing unit (sensing unit). That is, when the fingertip is brought into contact with the touch panel, the mutual capacitance between the detection electrode 14 and the other electrode changes, and the position of the fingertip is calculated by an IC (integrated circuit) circuit based on the change amount.
The detection electrode 14 has a role of detecting an input position in the X direction of an operator's finger approaching the central region E I and has a function of generating a capacitance between the detection electrode 14 and the finger. . The detection electrodes 14 are electrodes that extend in a first direction (X direction) and are arranged at a predetermined interval in a second direction (Y direction) orthogonal to the first direction. In FIG. 1, five detection electrodes 14 are provided, but the number thereof is not particularly limited, and a plurality of detection electrodes 14 may be provided.
In FIG. 1, the detection electrode 14 is a solid film, but may include a predetermined pattern such as a mesh shape.
 検出電極14を構成する材料は特に制限されず、例えば、酸化インジウムスズ(ITO)、酸化スズ、酸化亜鉛、酸化カドミウム、酸化ガリウム、酸化チタンなどの金属酸化物が挙げられる。また、金(Au)、銀(Ag)、銅(Cu)、アルミニウム(Al)などの金属や合金などを使用してもよい。
 検出電極14の形成方法は特に制限されず、公知の方法を採用できるが、例えば、スパッタリング法または蒸着法により形成されることが好ましい。
The material that constitutes the detection electrode 14 is not particularly limited, and examples thereof include metal oxides such as indium tin oxide (ITO), tin oxide, zinc oxide, cadmium oxide, gallium oxide, and titanium oxide. Alternatively, a metal or an alloy such as gold (Au), silver (Ag), copper (Cu), or aluminum (Al) may be used.
The method for forming the detection electrode 14 is not particularly limited, and a known method can be adopted, but it is preferably formed by, for example, a sputtering method or a vapor deposition method.
 なお、図1には図示しないが、引き出し配線18の他端(検出電極14側ではない端部)が位置する場所には、フレキシブルプリント配線板などが配置されていてもよい。フレキシブルプリント配線板は、基板上に複数の配線および端子が設けられた板であり、引き出し配線18のそれぞれの他端に接続され、静電容量式タッチパネルセンサーと外部の装置(例えば、表示装置)とを接続する役割を果たす。 Although not shown in FIG. 1, a flexible printed wiring board or the like may be disposed at a location where the other end of the lead-out wiring 18 (an end portion not on the detection electrode 14 side) is located. The flexible printed wiring board is a board in which a plurality of wirings and terminals are provided on a substrate, and is connected to each other end of the lead-out wiring 18, and a capacitive touch panel sensor and an external device (for example, a display device). Play a role in connecting.
[タッチパネルセンサー用導電性フィルムの製造方法]
 上述したタッチパネルセンサー用導電性フィルム10の製造方法は特に制限されず、公知の方法が採用されるが、主に、以下の2つの方法が挙げられる。
(方法1):基板12上に検出電極14を所定の位置に配置した後、基板12上にパターン状被めっき層16を所定の位置に配置して、パターン状被めっき層16上に引き出し配線18を配置し、その後、導電性接続部24を配置する方法
(方法2):基板12上にパターン状被めっき層16を所定の位置に配置した後、パターン状被めっき層16上に引き出し配線18を配置して、その後、基板12上に検出電極14を所定の位置に配置し、その後、導電性接続部24を配置する方法
 上記方法1および方法2にて、パターン状被めっき層16および引き出し配線18を製造する手順としては、上述した[パターン状被めっき層および引き出し配線の製造方法]にて説明した手順が実施されることが好ましい。
[Method for producing conductive film for touch panel sensor]
Although the manufacturing method of the conductive film 10 for touch panel sensors mentioned above is not restrict | limited in particular, Although a well-known method is employ | adopted, the following two methods are mainly mentioned.
(Method 1): After the detection electrode 14 is arranged on the substrate 12 at a predetermined position, the patterned plating layer 16 is arranged on the substrate 12 at a predetermined position, and the lead wiring is formed on the patterned plating layer 16. 18 is disposed, and then the conductive connection portion 24 is disposed (method 2): after the patterned plated layer 16 is disposed on the substrate 12 at a predetermined position, the lead wiring is disposed on the patterned plated layer 16. 18 and then, the method of disposing the detection electrode 14 at a predetermined position on the substrate 12 and then disposing the conductive connection portion 24. In the above method 1 and method 2, the patterned plated layer 16 and As a procedure for manufacturing the lead wiring 18, it is preferable that the procedure described in the above-mentioned “Method for manufacturing a patterned plated layer and a lead wiring” is performed.
 上述したタッチパネルセンサー用導電性フィルム10はタッチパネルセンサーに好適に使用することができる。
 例えば、2枚のタッチパネルセンサー用導電性フィルム(フィルムAおよびフィルムB)を用意して、フィルムA中の検出電極14およびフィルムB中の検出電極14が対向し、かつ、フィルムA中の検出電極14とフィルムB中の検出電極14とが直交するように、フィルムAとフィルムBとを粘着剤を貼り合せて、必要に応じて、他の部材(例えば、フレキシブルプリント配線基板)を接続し、静電容量式のタッチパネルセンサーを得ることができる。
 また、2枚のタッチパネルセンサー用導電性フィルム(フィルムAおよびフィルムB)を用意して、フィルムA中の検出電極14およびフィルムB中の基板12が対向し、かつ、フィルムA中の検出電極14とフィルムB中の検出電極14とが直交するように、フィルムAとフィルムBとを粘着剤を貼り合せて、必要に応じて、他の部材(例えば、フレキシブルプリント配線基板)を接続し、静電容量式のタッチパネルセンサーを得ることもできる。
 上記のようなタッチパネルセンサーは、タッチパネル(特に、静電容量式タッチパネル)に好適に適用できる。
The conductive film 10 for a touch panel sensor described above can be suitably used for a touch panel sensor.
For example, two conductive films (film A and film B) for a touch panel sensor are prepared, the detection electrode 14 in the film A and the detection electrode 14 in the film B are opposed, and the detection electrode in the film A 14 and the detection electrode 14 in the film B are orthogonally bonded to each other by attaching an adhesive to the film A and the film B, and, if necessary, connecting other members (for example, a flexible printed circuit board), A capacitive touch panel sensor can be obtained.
In addition, two conductive films (film A and film B) for the touch panel sensor are prepared, and the detection electrode 14 in the film A and the substrate 12 in the film B are opposed to each other, and the detection electrode 14 in the film A is provided. The film A and the film B are bonded with an adhesive so that the detection electrode 14 in the film B and the detection electrode 14 are orthogonal to each other, and another member (for example, a flexible printed wiring board) is connected as necessary. A capacitive touch panel sensor can also be obtained.
The touch panel sensor as described above can be suitably applied to a touch panel (in particular, a capacitive touch panel).
<<第2実施形態>>
 図5に、本発明のタッチパネルセンサー用導電性フィルムの第2実施形態の平面図を示す。図6は、切断線C-Cに沿って切断した断面図である。
 図5に示すタッチパネルセンサー用導電性フィルム100は、基板12と、基板12の一方の主面上(表面上)に配置された、検出電極14と、パターン状被めっき層160と、引き出し配線18と、導電性接続部24とを備える。なお、図5において、パターン状被めっき層160は、外側領域EO全域にわたって配置される。言い換えれば、中央領域EI以外の基板12の表面上にパターン状被めっき層160が配置される。
 図5に示すタッチパネルセンサー用導電性フィルム100は、パターン状被めっき層160の配置位置の点を除いて、図1に示すタッチパネルセンサー用導電性フィルム10と同様の構成を有するものであるので、同一の構成要素には同一の参照符号を付し、その説明を省略し、以下、主に、パターン状被めっき層160について詳述する。
<< Second Embodiment >>
In FIG. 5, the top view of 2nd Embodiment of the conductive film for touchscreen sensors of this invention is shown. FIG. 6 is a cross-sectional view taken along the cutting line CC.
The conductive film 100 for a touch panel sensor shown in FIG. 5 includes a substrate 12, a detection electrode 14, a patterned plated layer 160, and a lead wiring 18 disposed on one main surface (surface) of the substrate 12. And a conductive connection portion 24. In FIG. 5, the patterned plated layer 160 is disposed over the entire outer region E 2 O. In other words, the patterned plated layer 160 is disposed on the surface of the substrate 12 other than the central region E I.
Since the conductive film 100 for a touch panel sensor shown in FIG. 5 has the same configuration as that of the conductive film 10 for a touch panel sensor shown in FIG. The same reference numerals are assigned to the same components, and the description thereof is omitted. Hereinafter, the patterned plated layer 160 will be mainly described in detail.
 パターン状被めっき層160は、第1実施形態にて説明したパターン状被めっき層16と同様の構成を有し、基板12上での配置位置のみが異なる。
 パターン状被めっき層160の形成方法としては、上述した第1実施形態で説明したパターン状被めっき層16の形成方法と同様の手順が挙げられ、上述した[工程1:パターン状被めっき層形成工程]でのエネルギーを付与する領域を外側領域EO全域となるようにすればよい。
 本実施形態において、引き出し配線18の製造方法は特に制限されないが、以下の工程3(引き出し配線形成工程)が好適に挙げられる。以下、工程3の手順について詳述する。
The patterned plated layer 160 has the same configuration as the patterned plated layer 16 described in the first embodiment, and differs only in the arrangement position on the substrate 12.
Examples of the method for forming the patterned plated layer 160 include the same procedure as the method for forming the patterned plated layer 16 described in the first embodiment, and the above-described [Step 1: Patterned plated layer formation]. What is necessary is just to make it the area | region which assign | provides the energy in a process become the whole outer area | region EO .
In the present embodiment, the manufacturing method of the lead wiring 18 is not particularly limited, but the following process 3 (drawing wiring forming process) is preferably exemplified. Hereinafter, the procedure of step 3 will be described in detail.
[工程3:引き出し配線形成工程]
 工程3は、パターン状被めっき層にめっき触媒またはその前駆体を付与して、めっき触媒またはその前駆体が付与された被めっき層に対してめっき処理を行い、パターン状被めっき層上に金属層を形成し、得られた金属層をパターン状にエッチングして引き出し配線を形成する工程である。より具体的には、まず、図7(A)に示すように、パターン状被めっき層160が配置された基板12を用意し、次に、図7(B)に示すように、パターン状被めっき層160にめっき触媒またはその前駆体を付与して、めっき処理を実施してパターン状被めっき層160上に金属層30を形成し、次に、図7(C)に示すように、金属層30をパターン状にエッチングして引き出し配線18を得る。
[Step 3: Lead-out wiring formation step]
Step 3 applies a plating catalyst or a precursor thereof to the patterned layer to be plated, and performs a plating process on the layer to be plated to which the plating catalyst or the precursor has been applied. This is a step of forming a layer and etching the resulting metal layer into a pattern to form a lead-out wiring. More specifically, first, as shown in FIG. 7A, the substrate 12 on which the patterned plating layer 160 is arranged is prepared, and then, as shown in FIG. A plating catalyst or a precursor thereof is applied to the plating layer 160 and plating is performed to form the metal layer 30 on the patterned layer 160. Next, as shown in FIG. The lead wire 18 is obtained by etching the layer 30 into a pattern.
 本工程において、パターン状被めっき層160にめっき触媒またはその前駆体を付与して、めっき触媒またはその前駆体が付与されたパターン状被めっき層160に対してめっき処理を行い、パターン状被めっき層160上に金属層30を形成する工程の手順は、上述した第1実施形態で述べた工程2-1および工程2-2の手順と同じであるため、その詳細説明を省略する。
 以下では、金属層30をパターン状にエッチングして引き出し配線18を形成する工程の手順について詳述する。
In this step, a plating catalyst or a precursor thereof is applied to the patterned layer to be plated 160, and a plating treatment is performed on the patterned layer 160 to which the plating catalyst or its precursor has been applied. Since the procedure of forming the metal layer 30 on the layer 160 is the same as the procedure of the steps 2-1 and 2-2 described in the first embodiment, detailed description thereof is omitted.
Hereinafter, the procedure of the process of forming the lead wiring 18 by etching the metal layer 30 in a pattern will be described in detail.
 引き出し配線18の形成には、如何なる手法も使用することができ、具体的には一般的に知られているサブトラクティブ法(金属層上にパターン状のマスクを設け、マスクの非形成領域をエッチング処理した後、マスクを除去して、引き出し配線を形成する方法)、セミアディティブ法(金属層上にパターン状のマスクを設け、マスクの非形成領域に金属層を形成するようにめっき処理を行い、マスクを除去し、エッチング処理して、引き出し配線を形成する方法)が用いられる。
 サブトラクティブ法とは、具体的には、形成された金属層上にレジスト層を設けパターン露光、現像により形成される引き出し配線と同じパターンを形成し、レジストパターンをマスクとしてエッチング液で金属層を除去し、引き出し配線を形成する方法である。レジストとしては如何なる材料も使用でき、ネガ型、ポジ型、液状、フィルム状のものが使用できる。また、エッチング方法としては、プリント配線基板の製造時に使用されている方法が何れも使用可能であり、湿式エッチング、ドライエッチング等が使用可能であり、任意に選択すればよい。作業の操作上、湿式エッチングが装置などの簡便性の点で好ましい。エッチング液として、例えば、塩化第二銅、塩化第二鉄等の水溶液を使用することができる。
 セミアディティブ法とは、具体的には、形成された金属層上にレジスト層を設け、パターン露光、現像により非金属層パターン部と同じパターンを形成し、レジストパターンをマスクとして電解めっきを行い、レジストパターンを除去した後にクイックエッチングを実施し、金属層をパターン状に除去することで、引き出し配線を形成する方法である。レジスト、エッチング液等はサブトラクティブ法と同様な材料が使用できる。また、電解めっき処理の手法としては上記記載の手法が使用できる。
Any method can be used to form the lead-out wiring 18, and specifically, a generally known subtractive method (a patterned mask is provided on the metal layer, and a non-mask forming region is etched). After the treatment, the mask is removed and a lead wiring is formed), a semi-additive method (a patterned mask is provided on the metal layer, and a plating process is performed so as to form a metal layer in a non-mask formation region) , A method of removing the mask and performing etching to form a lead-out wiring).
Specifically, the subtractive method is to provide a resist layer on the formed metal layer, form the same pattern as the lead wiring formed by pattern exposure and development, and use the resist pattern as a mask to form the metal layer with an etching solution. This is a method of removing and forming a lead wiring. Any material can be used as the resist, and negative, positive, liquid, and film-like ones can be used. Moreover, as an etching method, any method used at the time of manufacturing a printed wiring board can be used, and wet etching, dry etching, and the like can be used, and may be arbitrarily selected. In terms of operation, wet etching is preferable from the viewpoint of simplicity of the apparatus. As an etching solution, for example, an aqueous solution of cupric chloride, ferric chloride, or the like can be used.
Specifically, the semi-additive method is to provide a resist layer on the formed metal layer, form the same pattern as the non-metal layer pattern portion by pattern exposure and development, and perform electrolytic plating using the resist pattern as a mask, This is a method of forming a lead-out wiring by performing quick etching after removing the resist pattern and removing the metal layer in a pattern. The resist, the etching solution, etc. can use the same material as the subtractive method. Moreover, the above-described method can be used as a method of electrolytic plating treatment.
 なお、上記金属層のエッチング処理を実施する際、必要に応じて、除去される金属層の直下に位置するパターン被めっき層中に含まれる金属イオンが還元して形成される金属粒子を合わせて除去してもよい。
 なお、上記金属粒子の除去方法は特に制限されず、使用されるエッチング液の種類や、エッチング時間を調整することにより、金属層の除去と共に金属粒子の除去も実施することができる。
In addition, when performing the etching process of the metal layer, the metal particles formed by reducing metal ions contained in the pattern plating layer located immediately below the metal layer to be removed are combined as necessary. It may be removed.
In addition, the removal method in particular of the said metal particle is not restrict | limited, The removal of a metal particle can also be implemented with the removal of a metal layer by adjusting the kind of etching liquid used, and etching time.
<<第3実施形態>>
 図8に、本発明のタッチパネルセンサー用導電性フィルムの第3実施形態の平面図を示す。図9は、切断線D-Dに沿って切断した断面図である。
 図8に示すタッチパネルセンサー用導電性フィルム200は、基板12と、基板12上に配置された被めっき層22と、被めっき層22上に配置された、検出電極14と、引き出し配線18と、導電性接続部24とを備える。図8においては、被めっき層22が基板12の表面全域に配置され、被めっき層22上に検出電極14および引き出し配線18が配置される。
 図8に示すタッチパネルセンサー用導電性フィルム200は、パターン状被めっき層16の代わりに被めっき層22を使用して、各部材の配置を変更した点を除いて、図1に示すタッチパネルセンサー用導電性フィルム10と同様の構成を有するものであるので、同一の構成要素には同一の参照符号を付し、その説明を省略し、以下、主に、被めっき層22について詳述する。
<< Third Embodiment >>
In FIG. 8, the top view of 3rd Embodiment of the conductive film for touchscreen sensors of this invention is shown. FIG. 9 is a cross-sectional view taken along the cutting line DD.
A conductive film 200 for a touch panel sensor shown in FIG. 8 includes a substrate 12, a plated layer 22 disposed on the substrate 12, a detection electrode 14 disposed on the plated layer 22, lead wires 18, And a conductive connection portion 24. In FIG. 8, the layer to be plated 22 is disposed over the entire surface of the substrate 12, and the detection electrode 14 and the lead wiring 18 are disposed on the layer to be plated 22.
The conductive film 200 for a touch panel sensor shown in FIG. 8 is for the touch panel sensor shown in FIG. 1 except that the plated layer 22 is used instead of the patterned plated layer 16 and the arrangement of each member is changed. Since it has the same configuration as that of the conductive film 10, the same reference numeral is given to the same component, the description thereof is omitted, and the plated layer 22 will be mainly described in detail below.
 被めっき層22と第1実施形態にて説明したパターン状被めっき層16とは、基板12上に配置される領域が異なるのみで、同一の構成を有する。具体的には、被めっき層22は、相互作用性基を有する。
 被めっき層22の形成方法は特に制限されず、上述した第1実施形態と同様の手順が挙げられ、上述した[工程1:パターン状被めっき層形成工程]でのエネルギーを付与する領域を基板12全域となるようにすればよい。
 また、引き出し配線18の製造方法は特に制限されないが、上述した第2実施形態で述べた工程3(引き出し配線形成工程)が好適に挙げられる。
The to-be-plated layer 22 and the pattern-like to-be-plated layer 16 demonstrated in 1st Embodiment differ in the area | region arrange | positioned on the board | substrate 12, and have the same structure. Specifically, the to-be-plated layer 22 has an interactive group.
The formation method of the to-be-plated layer 22 is not specifically limited, The procedure similar to 1st Embodiment mentioned above is mentioned, The area | region which provides the energy in the [process 1: patterned to-be-plated layer forming process] mentioned above is a board | substrate. What is necessary is just to become 12 whole areas.
Further, the method for manufacturing the lead wiring 18 is not particularly limited, but the step 3 (drawing wiring forming step) described in the second embodiment is preferable.
<<第4実施形態>>
 第1実施形態から第3実施形態においては、基板の片面に検出電極、パターン状被めっき層(または、被めっき層)、引き出し配線、および、導電性接続部が配置される態様について述べたが、基板の両面に検出電極、パターン状被めっき層(または、被めっき層)、引き出し配線、および、導電性接続部が配置されていてもよい。
 図10は、本発明のタッチパネルセンサー用導電性フィルムの第4実施形態の平面図を示す。図11は、切断線D-Dに沿って切断した断面図である。
 図10に示すように、タッチパネルセンサー用導電性フィルム300は、基板12と、基板12の両面上に配置される、検出電極14と、パターン状被めっき層16と、引き出し配線18と、導電性接続部24とを備える。なお、図10に示すように、基板12の表面上に配置される検出電極14と、基板12の裏面に配置される検出電極14とは、直交するように配置される。
<< Fourth Embodiment >>
In the first to third embodiments, the mode in which the detection electrode, the patterned layer to be plated (or the layer to be plated), the lead-out wiring, and the conductive connection portion are arranged on one surface of the substrate has been described. The detection electrode, the patterned plated layer (or plated layer), the lead-out wiring, and the conductive connection portion may be disposed on both surfaces of the substrate.
FIG. 10: shows the top view of 4th Embodiment of the conductive film for touchscreen sensors of this invention. FIG. 11 is a cross-sectional view taken along the cutting line DD.
As shown in FIG. 10, the conductive film 300 for a touch panel sensor includes a substrate 12, a detection electrode 14 disposed on both surfaces of the substrate 12, a patterned plated layer 16, lead wires 18, and conductivity. And a connection unit 24. As shown in FIG. 10, the detection electrode 14 disposed on the front surface of the substrate 12 and the detection electrode 14 disposed on the back surface of the substrate 12 are disposed so as to be orthogonal to each other.
 以下、実施例により、本発明についてさらに詳細に説明するが、本発明はこれらに限定されるものではない。 Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these.
(合成例:ポリマー1)
 2Lの三口フラスコに酢酸エチル1L、2-アミノエタノール159gを入れ、氷浴にて冷却した。そこへ、2-ブロモイソ酪酸ブロミド150gを内温20℃以下になるように調節して滴下した。その後、内温を室温(25℃)まで上昇させて2時間反応させた。反応終了後、蒸留水300mLを追加して反応を停止させた。その後、酢酸エチル相を蒸留水300mLで4回洗浄後、硫酸マグネシウムで乾燥し、さらに酢酸エチルを留去することで原料Aを80g得た。
 次に、500mLの三口フラスコに、原料A47.4g、ピリジン22g、酢酸エチル150mLを入れて氷浴にて冷却した。そこへ、アクリル酸クロライド25gを内温20℃以下になるように調節して滴下した。その後、室温に上げて3時間反応させた。反応終了後、蒸留水300mLを追加し、反応を停止させた。その後、酢酸エチル相を蒸留水300mLで4回洗浄後、硫酸マグネシウムで乾燥し、さらに酢酸エチルを留去した。その後、カラムクロマトグラフィーにて、以下のモノマーM1(20g)を得た。
(Synthesis example: Polymer 1)
1 L of ethyl acetate and 159 g of 2-aminoethanol were placed in a 2 L three-necked flask and cooled in an ice bath. Thereto, 150 g of 2-bromoisobutyric acid bromide was added dropwise while adjusting the internal temperature to 20 ° C. or less. Thereafter, the internal temperature was raised to room temperature (25 ° C.) and reacted for 2 hours. After completion of the reaction, 300 mL of distilled water was added to stop the reaction. Thereafter, the ethyl acetate phase was washed four times with 300 mL of distilled water, dried over magnesium sulfate, and 80 g of raw material A was obtained by distilling off ethyl acetate.
Next, 47.4 g of raw material A, 22 g of pyridine, and 150 mL of ethyl acetate were placed in a 500 mL three-necked flask and cooled in an ice bath. Thereto, 25 g of acrylic acid chloride was added dropwise while adjusting the internal temperature to 20 ° C. or lower. Then, it was raised to room temperature and reacted for 3 hours. After completion of the reaction, 300 mL of distilled water was added to stop the reaction. Thereafter, the ethyl acetate phase was washed four times with 300 mL of distilled water and then dried over magnesium sulfate, and further ethyl acetate was distilled off. Thereafter, the following monomer M1 (20 g) was obtained by column chromatography.
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000006
 500mLの三口フラスコに、N,N-ジメチルアセトアミド8gを入れ、窒素気流下、65℃まで加熱した。そこへ、モノマーM1:14.3g、アクリロニトリル(東京化成工業(株)製)3.0g、アクリル酸(東京化成製)6.5g、V-65(和光純薬製)0.4gのN,N-ジメチルアセトアミド8g溶液を、4時間かけて滴下した。
 滴下終了後、さらに反応溶液を3時間撹拌した。その後、N,N-ジメチルアセトアミド41gを追加し、室温まで反応溶液を冷却した。上記の反応溶液に、4-ヒドロキシTEMPO(東京化成製)0.09g、DBU(ジアザビシクロウンデセン)54.8gを加え、室温で12時間反応を行った。その後、反応液に70質量%メタンスルホン酸水溶液54g加えた。反応終了後、水で再沈を行い、固形物を取り出し、ポリマー1を12g得た。
A 500 mL three-necked flask was charged with 8 g of N, N-dimethylacetamide and heated to 65 ° C. under a nitrogen stream. Thereto, monomer M1: 14.3 g, acrylonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) 3.0 g, acrylic acid (manufactured by Tokyo Chemical Industry) 6.5 g, V-65 (manufactured by Wako Pure Chemical Industries) 0.4 g of N, A solution of 8 g of N-dimethylacetamide was added dropwise over 4 hours.
After completion of the dropwise addition, the reaction solution was further stirred for 3 hours. Thereafter, 41 g of N, N-dimethylacetamide was added, and the reaction solution was cooled to room temperature. To the reaction solution, 0.09 g of 4-hydroxy TEMPO (manufactured by Tokyo Chemical Industry) and 54.8 g of DBU (diazabicycloundecene) were added and reacted at room temperature for 12 hours. Thereafter, 54 g of a 70 mass% methanesulfonic acid aqueous solution was added to the reaction solution. After completion of the reaction, reprecipitation was carried out with water, the solid matter was taken out, and 12 g of polymer 1 was obtained.
 得られたポリマー1の同定をIR(infrared)測定機((株)堀場製作所製)を用いて行った。測定はポリマーをアセトンに溶解させKBr結晶を用いて行った。IR測定の結果、2240cm-1付近にピークが観測されニトリルユニットであるアクリロニトリルがポリマーに導入されている事が分かった。また、酸価測定によりカルボン酸ユニットとしてアクリル酸が導入されている事が分かった。また、重DMSO(ジメチルスルホキシド)に溶解させ、ブルカー製300MHzのNMR(Nuclear Magnetic Resonance)(AV-300)にて測定を行った。ニトリル基含有ユニットに相当するピークが2.5-0.7ppm(5H分)にブロードに観察され、重合性基含有ユニットに相当するピークが7.8-8.1ppm(1H分)、5.8-5.6ppm(1H分)、5.4-5.2ppm(1H分)、4.2-3.9ppm(2H分)、3.3-3.5ppm(2H分)、2.5-0.7ppm(6H分)にブロードに観察され、カルボン酸含有ユニットに相当するピークが2.5-0.7ppm(3H分)にブロードに観察され、重合性基含有ユニット:ニトリル基含有ユニット:カルボン酸基ユニット=30:30:40(mol%)であることが分かった。 The obtained polymer 1 was identified using an IR (infrared) measuring machine (manufactured by Horiba, Ltd.). The measurement was performed by dissolving the polymer in acetone and using KBr crystals. As a result of IR measurement, a peak was observed in the vicinity of 2240 cm −1 , and it was found that acrylonitrile, which is a nitrile unit, was introduced into the polymer. Moreover, it was found from the acid value measurement that acrylic acid was introduced as a carboxylic acid unit. Further, it was dissolved in heavy DMSO (dimethyl sulfoxide) and measured by Bruker 300 MHz NMR (Nuclear Magnetic Resonance) (AV-300). 4. A peak corresponding to the nitrile group-containing unit is broadly observed at 2.5-0.7 ppm (5H min), and a peak corresponding to the polymerizable group-containing unit is 7.8-8.1 ppm (1H min). 8-5.6 ppm (1H min), 5.4-5.2 ppm (1H min), 4.2-3.9 ppm (2H min), 3.3-3.5 ppm (2H min), 2.5- A broad peak is observed at 0.7 ppm (6H min), and a peak corresponding to a carboxylic acid-containing unit is broadly observed at 2.5-0.7 ppm (3H min). A polymerizable group-containing unit: a nitrile group-containing unit: It was found that the carboxylic acid group unit = 30: 30: 40 (mol%).
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000007
<被めっき層形成用組成物の調製>
 マグネチックスターラーを入れた200mlビーカーに、水(18.95質量部)、プロピレングリコールモノメチルエーテル(75.8質量部)、ポリマー1(5質量部)、および、IRGACUREOXE02(BASF社製)(0.25質量部)を加えて、調液し、被めっき層形成用組成物を得た。
<Preparation of composition for forming layer to be plated>
In a 200 ml beaker containing a magnetic stirrer, water (18.95 parts by mass), propylene glycol monomethyl ether (75.8 parts by mass), polymer 1 (5 parts by mass), and IRGACUREOXE02 (manufactured by BASF) (0. 0 parts). 25 parts by mass) was added to prepare a composition for forming a layer to be plated.
<実施例1>
 ガラス基板(コーニンング製)を150℃にて1時間加熱乾燥させた後、ガラス基板上にプライマー層形成用組成物(Nipol1561(日本ゼオン製)水分散溶液(全固形分濃度40.5質量部))を1500rpmにて1分間スピンコートして、120℃で30分乾燥させて、プライマー層を形成した。続いて、プライマー層上に、被めっき層形成用組成物をスピンコートして、80℃にて5分間乾燥させた。その後、ライン/スペースが3μm/3μmのパターンを有するネガ型用のマスク越しに基板を大気下にてUV照射(エネルギー量:2J、10mW、波長:256nm)し、1%の炭酸水素ナトリウムを用いて現像することでパターン状被めっき層(厚み:0.25μm)を形成した。
 パターン状被めっき層を形成していないガラス基板の面を養生テープ(日東電工製)にてマスキングした後、パターン状被めっき層を有するガラス基板をPd触媒付与液MAT-2(上村工業製)のMAT-2Aのみを5倍に希釈したもの(触媒付与液、pH:3.5)に室温にて5分間浸漬し、純水にて2回洗浄した。次に、還元剤MAB(上村工業製)に36℃にて5分間浸漬し、純水にて2回洗浄した。その後、活性化処理液MEL-3(上村工業製)に室温にて5分間浸漬し、洗浄することなく無電解めっき液スルカップPEA(上村工業製)に室温にてそれぞれ60分浸漬した。マスキングしたテープを剥がし純水にて2回洗浄して、パターン状被めっき層上にパターン状銅層(引き出し配線に該当)を備えるガラス基板を得た。
<Example 1>
A glass substrate (manufactured by Corning) was heated and dried at 150 ° C. for 1 hour, and then a primer layer forming composition (Nipol 1561 (manufactured by ZEON Corporation) in water dispersion (total solid content concentration: 40.5 parts by mass) ) Was spin-coated at 1500 rpm for 1 minute and dried at 120 ° C. for 30 minutes to form a primer layer. Subsequently, the composition for forming a layer to be plated was spin-coated on the primer layer and dried at 80 ° C. for 5 minutes. After that, the substrate was irradiated with UV in the atmosphere (energy amount: 2J, 10 mW, wavelength: 256 nm) through a negative mask having a pattern of 3 μm / 3 μm line / space, and 1% sodium hydrogen carbonate was used. And developed to form a patterned plated layer (thickness: 0.25 μm).
After masking the surface of the glass substrate on which the patterned coating layer is not formed with a curing tape (manufactured by Nitto Denko), the glass substrate having the patterned coating layer is coated with Pd catalyst applying liquid MAT-2 (manufactured by Uemura Kogyo). Of MAT-2A alone (catalyst imparting solution, pH: 3.5) was immersed for 5 minutes at room temperature, and washed twice with pure water. Next, it was immersed in a reducing agent MAB (manufactured by Uemura Kogyo) at 36 ° C. for 5 minutes and washed twice with pure water. Thereafter, it was immersed in an activation treatment solution MEL-3 (manufactured by Uemura Kogyo) at room temperature for 5 minutes, and immersed in electroless plating solution Sulcup PEA (manufactured by Uemura Kogyo) for 60 minutes at room temperature without washing. The masked tape was peeled off and washed twice with pure water to obtain a glass substrate provided with a patterned copper layer (corresponding to a lead-out wiring) on the patterned plated layer.
 次に、得られたガラス基板上のパターン状銅層が配置されていない領域に、酸化インジウムと酸化錫が重量比95:5の組成で充填密度98%の酸化インジウム-酸化錫ターゲットを用いるスパッタリング法によってITO層を形成し、フォトリソグラフィー法でレジストパターニング、エッチングして、パターン状のITO層(検出電極に該当)を得た。
 さらに、パターン状銅層とITO層との間に、銀ナノ粒子を含む導電性インク(ハリマ化成製 NPS-JL)をインクジェット法にて滴下して、加熱硬化処理を実施して、パターン状銅層とITO層とを電気的に接続する、銀からなる導電性接続部を形成し、導電性フィルムを得た。
Next, sputtering using an indium oxide-tin oxide target having a composition of indium oxide and tin oxide at a weight ratio of 95: 5 and a packing density of 98% is applied to a region where the patterned copper layer on the glass substrate is not disposed. An ITO layer was formed by the method, and resist patterning and etching were performed by a photolithography method to obtain a patterned ITO layer (corresponding to a detection electrode).
Furthermore, conductive ink containing silver nanoparticles (NPS-JL manufactured by Harima Chemicals Co., Ltd.) is dropped between the patterned copper layer and the ITO layer by an inkjet method, and heat-curing treatment is performed. A conductive connecting portion made of silver, which electrically connects the layer and the ITO layer, was formed to obtain a conductive film.
<実施例2>
 ガラス基板(コーニンング製)を150℃にて1時間加熱乾燥させた後、ガラス基板上にプライマー層形成用組成物(Nipol1561(日本ゼオン製)水分散溶液(全固形分濃度40.5質量部))を1500rpmにて1分間スピンコートして、120℃で30分乾燥させて、プライマー層を形成した。続いて、プライマー層上に、被めっき層形成用組成物をスピンコートして、80℃にて5分間乾燥させた。その後、塗膜全面に大気下にてUV照射(エネルギー量:2J、10mW、波長:256nm)し、被めっき層(厚み:0.25μm)を形成した。
 被めっき層を形成していないガラス基板の面を養生テープ(日東電工製)にてマスキングした後、被めっき層を有するガラス基板をPd触媒付与液MAT-2(上村工業製)のMAT-2Aのみを5倍に希釈したものに室温にて5分間浸漬し、純水にて2回洗浄した。次に、還元剤MAB(上村工業製)に36℃にて5分間浸漬し、純水にて2回洗浄した。その後、活性化処理液MEL-3(上村工業製)に室温にて5分間浸漬し、洗浄することなく無電解めっき液スルカップPEA(上村工業製)に室温にてそれぞれ60分浸漬した。マスキングしたテープを剥がし純水にて2回洗浄して、被めっき層上に銅層を備えるガラス基板を得た。
 得られた銅層上にドライレジストフィルム(日立化成製;RY3315、膜厚15μm)を真空ラミネーター(名機製作所製:MVLP-600)で70℃、0.2MPaでラミネートした。次いで、ドライレジストフィルムがラミネートされた基板に、JPCA-ET01に定める櫛型配線(JPCA-BU01-2007準拠)が形成できるガラスマスクを密着させ、レジストを中心波長405nmの露光機にて70mJの光エネルギーを照射した。露光後の基板に、1%Na2CO3水溶液を0.2MPaのスプレー圧で噴きつけ、現像を行なった。その後、基板の水洗・乾燥を行い、ライン/スペースが8μm/8μmのレジストパターンを形成した。
 レジストパターンを形成した基板を、FeCl3/HCl水溶液(エッチング液)に温度40℃で浸漬することによりエッチングを行い、レジストパターンの非形成領域に存在する銅層を除去した。その後、3%NaOH水溶液を0.2MPaのスプレー圧で基板上に噴き付けることで、レジストパターンを膨潤剥離し、10%硫酸水溶液で中和処理を行い、水洗することでパターン状銅層(引き出し配線に該当)を備えるガラス基板を得た。
 得られたガラス基板を用いて、実施例1と同様の手順に従って、パターン状のITO層および導電性接続部を形成し、導電性フィルムを得た。
<Example 2>
A glass substrate (manufactured by Corning) was heated and dried at 150 ° C. for 1 hour, and then a primer layer forming composition (Nipol 1561 (manufactured by ZEON Corporation) in water dispersion (total solid content concentration: 40.5 parts by mass) ) Was spin-coated at 1500 rpm for 1 minute and dried at 120 ° C. for 30 minutes to form a primer layer. Subsequently, the composition for forming a layer to be plated was spin-coated on the primer layer and dried at 80 ° C. for 5 minutes. Thereafter, UV irradiation (energy amount: 2 J, 10 mW, wavelength: 256 nm) was performed on the entire surface of the coating film in the air to form a layer to be plated (thickness: 0.25 μm).
After masking the surface of the glass substrate on which the layer to be plated is formed with a curing tape (manufactured by Nitto Denko), the glass substrate having the layer to be plated is made of MAT-2A made of Pd catalyst application liquid MAT-2 (manufactured by Uemura Kogyo). No. 5 was diluted 5 times at room temperature and washed twice with pure water. Next, it was immersed in a reducing agent MAB (manufactured by Uemura Kogyo) at 36 ° C. for 5 minutes and washed twice with pure water. Thereafter, it was immersed in an activation treatment solution MEL-3 (manufactured by Uemura Kogyo) at room temperature for 5 minutes, and immersed in electroless plating solution Sulcup PEA (manufactured by Uemura Kogyo) for 60 minutes at room temperature without washing. The masked tape was peeled off and washed twice with pure water to obtain a glass substrate having a copper layer on the layer to be plated.
A dry resist film (manufactured by Hitachi Chemical; RY3315, film thickness: 15 μm) was laminated on the obtained copper layer with a vacuum laminator (manufactured by Meiki Seisakusho: MVLP-600) at 70 ° C. and 0.2 MPa. Next, a glass mask capable of forming a comb-type wiring (compliant with JPCA-BU01-2007) as defined in JPCA-ET01 is closely attached to the substrate on which the dry resist film is laminated, and the resist is exposed to light of 70 mJ with an exposure machine having a central wavelength of 405 nm. Irradiated with energy. Development was performed by spraying a 1% Na 2 CO 3 aqueous solution onto the exposed substrate at a spray pressure of 0.2 MPa. Thereafter, the substrate was washed with water and dried to form a resist pattern having a line / space of 8 μm / 8 μm.
Etching was performed by immersing the substrate on which the resist pattern was formed in an FeCl 3 / HCl aqueous solution (etching solution) at a temperature of 40 ° C. to remove the copper layer present in the region where the resist pattern was not formed. Thereafter, the resist pattern is swollen and peeled off by spraying a 3% NaOH aqueous solution onto the substrate at a spray pressure of 0.2 MPa, neutralized with a 10% sulfuric acid aqueous solution, and washed with water to form a patterned copper layer (drawer). A glass substrate provided with a wiring) was obtained.
Using the obtained glass substrate, according to the same procedure as in Example 1, a patterned ITO layer and a conductive connection part were formed to obtain a conductive film.
<比較例1>
 パターン状銅層の代わりに、導電性インク(ハリマ化成社製 NPS-JL)を用いて、インクジェット法(FUJIFILM Dimatix社製 DMP2831)にてパターン状銀層(引き出し配線に該当)を作製した以外は、実施例1と同様の手順に従って、導電性フィルムを得た。
 ただし、導電性インクを用いたインクジェット法では、装置の性能上の問題から、ライン/スペースが100μm/100μmのパターン状銀層しか得られなかった。
<Comparative Example 1>
Except that a patterned silver layer (corresponding to a lead-out wiring) was produced by an inkjet method (DMP2831 made by FUJIFILM Dimatix) using conductive ink (NPS-JL made by Harima Chemicals Co., Ltd.) instead of the patterned copper layer According to the same procedure as in Example 1, a conductive film was obtained.
However, in the ink jet method using conductive ink, only a patterned silver layer having a line / space of 100 μm / 100 μm was obtained due to a problem in the performance of the apparatus.
<微細化評価>
 実施例1および2のパターン状銅層、および、比較例1のパターン状銀層のライン/スペースの大きさに関して、以下の基準に沿って評価した。
「A」:ライン/スペースの幅がともに5μm以下のパターンが形成可能な場合
「B」:ライン/スペースの幅がともに5μm超10μm以下のパターンが形成可能な場合
「C」:ライン/スペースの幅がともに10μm超のパターンしか形成できない場合
<Miniaturization evaluation>
The line / space sizes of the patterned copper layers of Examples 1 and 2 and the patterned silver layer of Comparative Example 1 were evaluated according to the following criteria.
“A”: When a line / space width of 5 μm or less can be formed “B”: A line / space width of both 5 μm and 10 μm or less can be formed “C”: Line / space When only patterns with a width exceeding 10 μm can be formed
<密着性評価>
(テープ剥離試験)
 評価方法としては、実施例1および2のパターン状銅層、および、比較例1のパターン状銀層を形成後にテープ剥離試験を行い、パターン状銅層またはパターン状銀層が剥離せずに基板上に残った残存率を以下の基準に沿って評価した。
 なお、テープ剥離試験は、JIS K5600-5-6に従って、実施した。
「A」:90~100%残存した場合
「B」:10%を超えて剥離した場合
<Adhesion evaluation>
(Tape peeling test)
As an evaluation method, a tape peeling test was performed after the patterned copper layer of Examples 1 and 2 and the patterned silver layer of Comparative Example 1 were formed, and the patterned copper layer or the patterned silver layer was not peeled off. The residual rate remaining above was evaluated according to the following criteria.
The tape peeling test was performed according to JIS K5600-5-6.
“A”: 90 to 100% remaining “B”: More than 10% peeled
<接続性評価>
(接続抵抗測定)
 評価方法としては、上記パターン状銅層(または、パターン状銀層)とパターン状ITO層間の抵抗値を測定(日置電機社製、ミリオームハイテスタ3540)し、以下の基準に沿って評価した。
「A」:抵抗値が10mΩ以下の場合
「B」:抵抗値が10mΩを超える場合
「C」:抵抗値が測定出来ず、実質的に断線している場合
<Connectivity evaluation>
(Connection resistance measurement)
As an evaluation method, a resistance value between the patterned copper layer (or patterned silver layer) and the patterned ITO layer was measured (manufactured by Hioki Electric Co., Ltd., milliohm high tester 3540), and evaluated according to the following criteria.
“A”: When the resistance value is 10 mΩ or less “B”: When the resistance value exceeds 10 mΩ “C”: When the resistance value cannot be measured and is substantially disconnected
 上記評価結果を表1にまとめて示す。
 なお、表1中、「処理方法」欄の「X」はパターン状被めっき層上にパターン状銅層を形成する方法を意図し、「Y」は銅層をエッチングしてパターン状銅層を形成する方法を意図する。
The evaluation results are summarized in Table 1.
In Table 1, “X” in the “Treatment Method” column means a method of forming a patterned copper layer on the patterned layer to be plated, and “Y” indicates that the patterned copper layer is etched by etching the copper layer. Intended for the method of forming.
Figure JPOXMLDOC01-appb-T000008
Figure JPOXMLDOC01-appb-T000008
 上記実施例1および2に示すように、本発明のタッチパネルセンサー用導電性フィルム中のパターン状銅層(引き出し配線に該当)は微細化が可能であると共に、密着性にも優れていた。また、パターン状銅層とITO層(検出電極に該当)との電気的接続性も高かった。
 一方、導電性インクを用いた比較例1においては、そもそもパターン状銀層(引き出し配線に該当)の微細化ができず、かつ、形成されたパターン状銀層の密着性も劣っていた。
As shown in Examples 1 and 2, the patterned copper layer (corresponding to the lead-out wiring) in the conductive film for a touch panel sensor of the present invention can be miniaturized and has excellent adhesion. Moreover, the electrical connectivity between the patterned copper layer and the ITO layer (corresponding to the detection electrode) was also high.
On the other hand, in Comparative Example 1 using conductive ink, the patterned silver layer (corresponding to the lead-out wiring) could not be refined in the first place, and the adhesiveness of the formed patterned silver layer was inferior.
<実施例3>
 ガラス基板(コーニンング製)を150℃にて1時間加熱乾燥させた後、ガラス基板上にプライマー層形成用組成物(Nipol1561(日本ゼオン製)水分散溶液(全固形分濃度40.5質量部))を1500rpmにて1分間スピンコートして、120℃で30分乾燥させて、プライマー層を形成した。続いて、プライマー層上に被めっき層形成用組成物を1500rpmにて1分間スピンコートして、80℃にて5分間乾燥させた。その後、所定のネガ型用のマスク越しに基板を大気下にてUV照射(エネルギー量:2J、10mW、波長:256nm)し、1%の炭酸水素ナトリウムを用いて現像することで、図1のパターン状被めっき層16と同様の位置に、パターン状被めっき層を形成した。
 得られたパターン状被めっき層を有するガラス基板を用いて、実施例1と同様の手順に従って、パターン状被めっき層上にパターン状銅層を作製した。得られたパターン状銅層は、図1の引き出し配線18と同様の位置に配置される。
 次に、図1の検出電極14の位置にITO層が配置されるように、スパッタリング法、フォトリソグラフィー法により、ITO層を作製した。
 さらに、図1の導電性接続部24が形成されるように、パターン状銅層とITO層との間に、銀ナノ粒子を含む導電性インク(ハリマ化成社製 NPS-JL)をインクジェット法にて滴下して、加熱硬化処理を実施して、銀からなる導電性接続部を形成した。
 なお、得られたタッチパネル用導電性フィルムは、実施例1と同様に、所望の効果(微細化、低抵抗性、高密着性)を示した。
<Example 3>
A glass substrate (manufactured by Corning) was heated and dried at 150 ° C. for 1 hour, and then a primer layer forming composition (Nipol 1561 (manufactured by ZEON Corporation) in water dispersion (total solid content concentration: 40.5 parts by mass) ) Was spin-coated at 1500 rpm for 1 minute and dried at 120 ° C. for 30 minutes to form a primer layer. Subsequently, the composition for forming a layer to be plated was spin-coated on the primer layer at 1500 rpm for 1 minute and dried at 80 ° C. for 5 minutes. Thereafter, the substrate is irradiated with UV light (energy amount: 2J, 10 mW, wavelength: 256 nm) in the air through a predetermined negative mask, and developed with 1% sodium hydrogen carbonate, thereby developing the substrate shown in FIG. A patterned plated layer was formed at the same position as the patterned plated layer 16.
A patterned copper layer was produced on the patterned plated layer according to the same procedure as in Example 1 using the obtained glass substrate having the patterned plated layer. The obtained patterned copper layer is disposed at the same position as the lead-out wiring 18 in FIG.
Next, an ITO layer was produced by sputtering or photolithography so that the ITO layer was disposed at the position of the detection electrode 14 in FIG.
Further, a conductive ink containing silver nanoparticles (NPS-JL manufactured by Harima Kasei Co., Ltd.) is used in the inkjet method between the patterned copper layer and the ITO layer so that the conductive connection portion 24 of FIG. 1 is formed. Then, a heat curing treatment was performed to form a conductive connection portion made of silver.
In addition, the obtained conductive film for a touch panel showed desired effects (miniaturization, low resistance, high adhesion) as in Example 1.
 また、図5のパターン状被めっき層160と同様の位置に、パターン状被めっき層を形成した以外は、上記と同様の手順に従って、タッチパネル用導電性フィルムを得た。
 さらに、上記手順をガラス基板の両面に実施することにより、図10に示す態様のタッチパネル用導電性フィルムを得た。
Moreover, the conductive film for touchscreens was obtained according to the procedure similar to the above except having formed the pattern-like to-be-plated layer in the same position as the pattern-like to-be-plated layer 160 of FIG.
Furthermore, the conductive film for touch panels of the aspect shown in FIG. 10 was obtained by implementing the said procedure on both surfaces of a glass substrate.
 10,100,200,300  タッチパネルセンサー用導電性フィルム
 12  基板
 14  検出電極
 16,160  パターン状被めっき層
 18  引き出し配線
 20  塗膜
 22  被めっき層
 24  導電性接続部
 30  金属層
 
10, 100, 200, 300 Conductive film for touch panel sensor 12 Substrate 14 Detection electrode 16,160 Patterned layer to be plated 18 Lead-out wiring 20 Coating layer 22 Plated layer 24 Conductive connection 30 Metal layer

Claims (9)

  1.  基板と、
     前記基板の少なくとも一方の表面上に配置された検出電極と、
     前記基板の前記検出電極がある側の表面上で、前記検出電極の周辺に配置され、めっき触媒またはその前駆体と相互作用する官能基を有するパターン状被めっき層と、
     前記パターン状被めっき層上に配置された引き出し配線と、
     前記検出電極と前記引き出し配線とを電気的に接続する導電性接続部とを備え、
     前記引き出し配線が、前記パターン状被めっき層にめっき触媒またはその前駆体を付与して、前記めっき触媒またはその前駆体が付与されたパターン状被めっき層に対してめっき処理を行う工程を少なくとも有する方法により形成された配線である、タッチパネルセンサー用導電性フィルム。
    A substrate,
    A detection electrode disposed on at least one surface of the substrate;
    On the surface of the substrate on the side where the detection electrode is located, a pattern-like plated layer disposed around the detection electrode and having a functional group that interacts with a plating catalyst or a precursor thereof;
    A lead-out line disposed on the patterned layer to be plated;
    A conductive connection portion for electrically connecting the detection electrode and the lead-out wiring;
    The lead-out wiring includes at least a step of applying a plating catalyst or a precursor thereof to the patterned plating layer and performing a plating process on the patterned plating layer provided with the plating catalyst or the precursor thereof. A conductive film for a touch panel sensor, which is a wiring formed by the method.
  2.  前記パターン状被めっき層が、めっき触媒またはその前駆体と相互作用する官能基および重合性基を有する化合物を含有する被めっき層形成用組成物に対してパターン状にエネルギーを付与して形成される層である、請求項1に記載のタッチパネルセンサー用導電性フィルム。 The patterned layer to be plated is formed by applying energy in a pattern to a composition for forming a layer to be plated containing a compound having a functional group and a polymerizable group that interacts with a plating catalyst or a precursor thereof. The conductive film for a touch panel sensor according to claim 1, wherein the conductive film is a layer.
  3.  基板と、
     前記基板上に配置された、めっき触媒またはその前駆体と相互作用する官能基を有する被めっき層と、
     前記被めっき層上に配置された検出電極と、
     前記被めっき層上で、前記検出電極の周辺に配置された引き出し配線と、
     前記検出電極と前記引き出し配線とを電気的に接続する導電性接続部とを備え、
     前記引き出し配線が、前記被めっき層にめっき触媒またはその前駆体を付与して、前記めっき触媒またはその前駆体が付与された被めっき層に対してめっき処理を行って金属層を形成し、前記金属層をパターン状にエッチングして形成される配線である、タッチパネルセンサー用導電性フィルム。
    A substrate,
    A layer to be plated having a functional group that interacts with the plating catalyst or a precursor thereof disposed on the substrate;
    A detection electrode disposed on the plated layer;
    On the plated layer, a lead-out wiring arranged around the detection electrode,
    A conductive connection portion for electrically connecting the detection electrode and the lead-out wiring;
    The lead-out wiring imparts a plating catalyst or a precursor thereof to the layer to be plated, performs a plating process on the layer to be plated with the plating catalyst or the precursor, and forms a metal layer, A conductive film for a touch panel sensor, which is a wiring formed by etching a metal layer in a pattern.
  4.  前記導電性接続部が、導電性ペーストまたは導電性インクを用いて印刷法により形成される接続部である、請求項1~3のいずれか1項に記載のタッチパネルセンサー用導電性フィルム。 The conductive film for a touch panel sensor according to any one of claims 1 to 3, wherein the conductive connection portion is a connection portion formed by a printing method using a conductive paste or conductive ink.
  5.  前記検出電極が、スパッタリング法または蒸着法により形成された電極である、請求項1~4のいずれか1項に記載のタッチパネルセンサー用導電性フィルム。 The conductive film for a touch panel sensor according to any one of claims 1 to 4, wherein the detection electrode is an electrode formed by a sputtering method or a vapor deposition method.
  6.  前記基板表面に隣接してプライマー層が配置される、請求項1~5のいずれか1項に記載のタッチパネルセンサー用導電性フィルム。 The conductive film for a touch panel sensor according to any one of claims 1 to 5, wherein a primer layer is disposed adjacent to the substrate surface.
  7.  前記引き出し配線の線幅が1~10μmである、請求項1~6のいずれか1項に記載のタッチパネルセンサー用導電性フィルム。 The conductive film for a touch panel sensor according to any one of claims 1 to 6, wherein a line width of the lead wiring is 1 to 10 µm.
  8.  請求項1~7のいずれか1項に記載のタッチパネルセンサー用導電性フィルムを含む、タッチパネルセンサー。 A touch panel sensor comprising the conductive film for a touch panel sensor according to any one of claims 1 to 7.
  9.  請求項1~7のいずれか1項に記載のタッチパネルセンサー用導電性フィルムを含む、タッチパネル。
     
    A touch panel comprising the conductive film for a touch panel sensor according to any one of claims 1 to 7.
PCT/JP2015/068930 2014-07-16 2015-07-01 Conductive film for touch panel sensor, touch panel sensor, and touch panel WO2016009829A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP2016534357A JP6279082B2 (en) 2014-07-16 2015-07-01 Conductive film for touch panel sensor, touch panel sensor, touch panel
CN201580028793.0A CN106462284B (en) 2014-07-16 2015-07-01 Contact panel sensor conductive film, contact panel sensor, touch panel

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2014-145826 2014-07-16
JP2014145826 2014-07-16

Publications (1)

Publication Number Publication Date
WO2016009829A1 true WO2016009829A1 (en) 2016-01-21

Family

ID=55078327

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2015/068930 WO2016009829A1 (en) 2014-07-16 2015-07-01 Conductive film for touch panel sensor, touch panel sensor, and touch panel

Country Status (4)

Country Link
JP (1) JP6279082B2 (en)
CN (1) CN106462284B (en)
TW (1) TW201614451A (en)
WO (1) WO2016009829A1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017169612A1 (en) * 2016-03-31 2017-10-05 富士フイルム株式会社 Electrically conductive laminate manufacturing method, laminate, and electrically conductive laminate
JP2022158850A (en) * 2021-03-31 2022-10-17 ティーピーケイ アドバンスド ソリューションズ インコーポレーテッド touch sensor

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI732892B (en) * 2016-07-26 2021-07-11 日商松下知識產權經營股份有限公司 Laminate board for see-through electrode, see-through electrode material, component, and method for manufacturing laminate board for see-through electrode

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006135271A (en) * 2003-11-27 2006-05-25 Fuji Photo Film Co Ltd Metallic pattern forming method, metallic pattern, and printed circuit board
JP2012119343A (en) * 2009-03-31 2012-06-21 Shibaura Mechatronics Corp Solar battery manufacturing method, solar battery manufacturing apparatus, and solar battery
WO2013018454A1 (en) * 2011-07-29 2013-02-07 富士フイルム株式会社 Composition for forming layer to be plated, and method of producing laminate having metal layer
JP2013102070A (en) * 2011-11-09 2013-05-23 Fujifilm Corp Method of manufacturing integrated solar cell
JP2013149232A (en) * 2011-12-22 2013-08-01 Fujifilm Corp Conductive sheet and touch panel
JP5421493B1 (en) * 2013-07-17 2014-02-19 富士フイルム株式会社 Laminate for touch panel, touch panel

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012163933A (en) * 2011-01-18 2012-08-30 Fujifilm Corp Conductive film and display device having the same
JP5849059B2 (en) * 2012-07-06 2016-01-27 富士フイルム株式会社 Conductive film for touch panel and touch panel
JP2014016589A (en) * 2012-07-11 2014-01-30 Dainippon Printing Co Ltd Polarizing plate-integrated conductive optical laminate and display device using the same
JP6278585B2 (en) * 2012-07-11 2018-02-14 大日本印刷株式会社 Multilayer transparent substrate, laminate using multilayer transparent substrate, and image display apparatus using them
JP6006187B2 (en) * 2013-08-30 2016-10-12 富士フイルム株式会社 Conductive film and method for producing the same

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006135271A (en) * 2003-11-27 2006-05-25 Fuji Photo Film Co Ltd Metallic pattern forming method, metallic pattern, and printed circuit board
JP2012119343A (en) * 2009-03-31 2012-06-21 Shibaura Mechatronics Corp Solar battery manufacturing method, solar battery manufacturing apparatus, and solar battery
WO2013018454A1 (en) * 2011-07-29 2013-02-07 富士フイルム株式会社 Composition for forming layer to be plated, and method of producing laminate having metal layer
JP2013102070A (en) * 2011-11-09 2013-05-23 Fujifilm Corp Method of manufacturing integrated solar cell
JP2013149232A (en) * 2011-12-22 2013-08-01 Fujifilm Corp Conductive sheet and touch panel
JP5421493B1 (en) * 2013-07-17 2014-02-19 富士フイルム株式会社 Laminate for touch panel, touch panel

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017169612A1 (en) * 2016-03-31 2017-10-05 富士フイルム株式会社 Electrically conductive laminate manufacturing method, laminate, and electrically conductive laminate
CN108884568A (en) * 2016-03-31 2018-11-23 富士胶片株式会社 Manufacturing method, laminated body and the conductive laminate of conductive laminate
JPWO2017169612A1 (en) * 2016-03-31 2019-01-31 富士フイルム株式会社 Method for manufacturing conductive laminate, laminate and conductive laminate
CN108884568B (en) * 2016-03-31 2020-06-02 富士胶片株式会社 Method for producing conductive laminate, and conductive laminate
JP2022158850A (en) * 2021-03-31 2022-10-17 ティーピーケイ アドバンスド ソリューションズ インコーポレーテッド touch sensor

Also Published As

Publication number Publication date
JPWO2016009829A1 (en) 2017-04-27
CN106462284A (en) 2017-02-22
JP6279082B2 (en) 2018-02-14
CN106462284B (en) 2019-04-23
TW201614451A (en) 2016-04-16

Similar Documents

Publication Publication Date Title
JP6340378B2 (en) Method for manufacturing conductive laminate, conductive laminate, touch sensor
JP6490192B2 (en) Touch sensor and touch panel
JP6490194B2 (en) Plating layer forming composition, plated layer precursor film, patterned film with plated layer, conductive film, touch panel
JP6145219B6 (en) Conductive laminate for touch panel, touch panel, transparent conductive laminate
JPWO2015190484A6 (en) Conductive laminate for touch panel, touch panel, transparent conductive laminate
JP2010185128A (en) Photosensitive resin composition for plating, laminate, method of producing surface metal film material using the same, surface metal film material, method of producing metal pattern material, metal pattern material, and wiring board
WO2016181824A1 (en) Conductive laminate manufacturing method, conductive laminate, substrate with plate-layer precursor layer, substrate with plate layer, and touch sensor
JP6275861B2 (en) Laminated body, conductive laminated body and manufacturing method thereof, touch panel sensor, touch panel, transfer film
JP6295330B2 (en) Conductive laminate for touch panel sensor, and manufacturing method thereof, touch panel sensor, touch panel
JP6402196B2 (en) Method for producing patterned layer-containing laminate, method for producing metal layer-containing laminate, touch panel sensor, touch panel, patterned layer-containing laminate, metal layer-containing laminate
JP6279082B2 (en) Conductive film for touch panel sensor, touch panel sensor, touch panel
JP2010077322A (en) Composition for forming plated layer, production method for metal pattern material and metal pattern material obtained thereby, and production method for surface metal film material and surface metal film material obtained thereby
WO2016158419A1 (en) Method of manufacturing conductive film for touch panel sensor, conductive film for touch panel sensor, and touch panel
WO2012133684A1 (en) Production method for laminate having patterned metal films, and plating layer-forming composition
WO2017170012A1 (en) Method for producing metal wiring line-containing laminate, metal wiring line-containing laminate, and substrate with layer to be plated
WO2012133032A1 (en) Production method for laminate having patterned metal films, and plating layer-forming composition
JP2011111602A (en) Insulating resin, insulating resin layer-forming composition, laminate, method for manufacturing surface metal film material, method for manufacturing metal pattern material, method for manufacturing wiring board, electronic part, and semiconductor device
JP5642378B2 (en) Insulating resin, insulating resin layer forming composition, laminate, surface metal film material manufacturing method, metal pattern material manufacturing method, wiring board manufacturing method, electronic component, semiconductor element
JP2012209387A (en) Manufacturing method of laminate having patterned metal film

Legal Events

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

Ref document number: 15821828

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2016534357

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 15821828

Country of ref document: EP

Kind code of ref document: A1