WO2017154786A1 - 被めっき層前駆体層付きフィルム、パターン状被めっき層付きフィルム、導電性フィルム、タッチパネル - Google Patents
被めっき層前駆体層付きフィルム、パターン状被めっき層付きフィルム、導電性フィルム、タッチパネル Download PDFInfo
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- WO2017154786A1 WO2017154786A1 PCT/JP2017/008551 JP2017008551W WO2017154786A1 WO 2017154786 A1 WO2017154786 A1 WO 2017154786A1 JP 2017008551 W JP2017008551 W JP 2017008551W WO 2017154786 A1 WO2017154786 A1 WO 2017154786A1
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- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06F—ELECTRIC DIGITAL DATA PROCESSING
- G06F2203/00—Indexing scheme relating to G06F3/00 - G06F3/048
- G06F2203/041—Indexing scheme relating to G06F3/041 - G06F3/045
- G06F2203/04103—Manufacturing, i.e. details related to manufacturing processes specially suited for touch sensitive devices
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/07—Treatments involving liquids, e.g. plating, rinsing
- H05K2203/0703—Plating
- H05K2203/072—Electroless plating, e.g. finish plating or initial plating
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material
- H05K3/181—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating
- H05K3/182—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating characterised by the patterning method
- H05K3/184—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating characterised by the patterning method using masks
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
- H05K3/381—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the substrate
Definitions
- the present invention relates to a film to be plated precursor layer, a film with a patterned layer to be plated, a conductive film, and a touch panel.
- a conductive film in which a conductive film (conductive thin wire) is disposed on a substrate is used in various applications.
- a conductive film conductive thin wire
- the demand for conductive films for capacitive touch panel sensors capable of multipoint detection has expanded rapidly. Yes.
- a method using a patterned plated layer For the formation of such a conductive film, for example, a method using a patterned plated layer has been proposed.
- a method for forming a conductive film “at least one functional group selected from the group consisting of an epoxy group, an amino group, a vinyl group, a mercapto group, an acryloyloxy group, a phenyl group, and a cyano group is included.
- a metal layer comprising: (3) and a step (4) of performing a plating process on the layer to be plated to which the plating catalyst or its precursor has been applied and forming a metal layer on the layer to be plated.
- the manufacturing method of the laminated body which has. "Is described.
- Patent Document 1 a primer layer is first formed on a substrate, and a precursor to be plated including a polymer having a functional group and a polymerizable group that interacts with the plating catalyst or a precursor thereof on the primer layer. A body layer is formed. Subsequently, after applying energy to this to-be-plated layer precursor and forming a pattern-like to-be-plated layer, the electrically conductive film is formed by providing a metal layer on the said pattern-like to-be-plated layer.
- Patent Document 1 describes that an elastomer is preferably used as the resin contained in the primer layer from the viewpoint of further improving the adhesion of the metal layer.
- the present invention provides a film with a plating layer precursor layer capable of forming a metal layer that is excellent in roll-to-roll manufacturability and has excellent adhesion to a substrate, and a patterned plating layer It is an object to provide an attached film. Another object of the present invention is to provide a conductive film and a touch panel.
- the inventors of the present invention have the characteristics of the undercoat layer in the film with the plated layer precursor layer, the surface hardness is 10 N / mm 2 or less, and the release paper.
- the inventors have found that the above problem can be solved when the friction coefficient is 5 or less, and have completed the present invention. That is, it has been found that the above object can be achieved by the following configuration.
- the undercoat layer has a to-be-plated layer precursor layer film having a hardness of 10 N / mm 2 or less on the surface and a friction coefficient of 5 or less with the release paper.
- Compound X a functional group that interacts with a plating catalyst or a precursor thereof, and a compound having a polymerizable group
- Composition Y a compound having a functional group that interacts with a plating catalyst or a precursor thereof, and a polymerizable group (3)
- the undercoat layer is a film with a patterned layer to be plated, having a hardness of 10 N / mm 2 or less on the surface and a friction coefficient of 5 or less with the release paper.
- the electroconductive film which has a film with a pattern-like to-be-plated layer as described in (3), and the metal layer arrange
- the film with a to-be-plated layer precursor layer which can form the metal layer excellent in the productivity by a roll to roll, and was excellent in the adhesiveness with a board
- FIG. 1 It is sectional drawing which shows typically an example of embodiment of the film with a to-be-plated layer precursor layer of this invention. It is sectional drawing which shows typically an example of embodiment of the electroconductive film of this invention. It is sectional drawing which shows typically an example of the process of hardening the coating film 30 in the film 10 with a to-be-plated layer precursor layer by exposure. It is sectional drawing which shows typically an example of the process of obtaining the film 50 with a pattern-form to-be-plated layer. It is sectional drawing which shows typically an example of the process of forming the metal layer 22 on the pattern-like to-be-plated layer 20, and obtaining the electroconductive film 100.
- FIG. 1 It is sectional drawing which shows typically an example of embodiment of the film with a to-be-plated layer precursor layer of this invention. It is sectional drawing which shows typically an example of embodiment of the electroconductive film of this invention. It is sectional drawing which shows typically an example of the process of hardening the coating film 30 in the film 10 with a to-be-
- a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
- active light or “radiation” refers to, for example, the emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer laser, extreme ultraviolet rays (EUV light), X-rays, and electron beams (EB). ) Etc.
- light means actinic rays or radiation.
- exposure in the present specification is not limited to exposure with a far ultraviolet ray, an extreme ultraviolet ray, an X-ray, an EUV light or the like represented by a mercury lamp or an excimer laser, but an electron beam, and In addition, drawing with a particle beam such as an ion beam is included in the exposure.
- the film substrate with a plated layer precursor layer of the present invention has a substrate, an undercoat layer disposed on the substrate, and a plated layer precursor layer disposed on the undercoat layer,
- the undercoat layer has a surface hardness (hereinafter also referred to as “surface hardness”) of 10 N / mm 2 or less and a coefficient of friction with the release paper of 5 or less.
- the surface hardness of the undercoat layer is determined as universal hardness (N / mm 2 ) by the following measurement method.
- (surface hardness) A spherical indenter with a radius of curvature of 0.2 mm is brought into contact with the surface of the undercoat layer (film thickness 2 ⁇ m) using a HM500 type film hardness meter manufactured by Fisher Instruments, and the universal hardness (N / Mm 2 ).
- the “friction coefficient” of the undercoat layer is determined by the following measurement method. (Coefficient of friction) The release paper is placed without applying force so that the release surface is in contact with the surface of the undercoat layer. Next, the load applied when a release paper is moved in the horizontal direction at a speed of 100 mm / min with a 100 g weight placed thereon is measured using a force gauge FGX-2 (manufactured by Nidec Symposium). . The friction coefficient is obtained by dividing the obtained measurement value (load) by the weight of the weight. In the evaluation test of the coefficient of friction, the therapy 38BKE (manufactured by Toray Industries, Inc.) was used as the “release paper”.
- the film with a to-be-plated layer precursor layer of the present invention can form a metal layer having excellent roll-to-roll manufacturability and excellent adhesion to the substrate by adopting the above configuration.
- the characteristic of the film with a to-be-plated layer precursor layer of the present invention is that the physical properties of the undercoat layer are such that the surface hardness is 10 N / mm 2 or less and the coefficient of friction with the release paper is 5 or less.
- the reason why the present inventors have difficulty in transporting a film using an elastomer resin as described in Patent Document 1 as an undercoat layer with a roll is that the undercoat layer is deformed when contacting the roll, I guess it is to stop the rotation of the roll.
- This phenomenon is particularly likely to occur when a film in which an undercoat layer formed of an elastomer is disposed on a substrate is rolled so that the undercoat layer is in contact with the roll.
- the plated layer precursor layer is used.
- the film thickness is small, the above-described conveyance failure tends to occur. This is considered to be because when the film thickness of the to-be-plated layer precursor layer is thin, it is easily influenced by the physical properties of the undercoat layer as a lower layer.
- a metal layer is formed on the undercoat layer via a patterned layer to be plated.
- the undercoat layer is formed of a rigid material that is not easily deformed by contact with a roll, it is difficult to relieve stress generated during the formation of the patterned plated layer and the metal layer, and the patterned plated layer and the undercoat layer And the interface between the patterned layer to be plated and the metal layer tend to peel off. That is, it is considered difficult to make the metal layer adhere well on the substrate.
- the present inventors have made various studies based on the above knowledge, thereby setting the physical properties of the undercoat layer to a surface hardness of 10 N / mm 2 or less and a coefficient of friction with the release paper of 5 or less. In some cases, it was clarified that the undercoat layer was not deformed even when contacted with the roll, and that the adhesion of the metal layer was excellent.
- FIG. 1 is a schematic cross-sectional view showing an example of an embodiment of a film with a precursor layer to be plated according to the present invention.
- a film 10 with a precursor layer to be plated in FIG. 1 includes a substrate 12, an undercoat layer 15 disposed on the substrate 12, and a precursor layer 30 to be plated disposed on the undercoat layer 15. Have.
- FIG. 1 is a schematic cross-sectional view showing an example of an embodiment of a film with a precursor layer to be plated according to the present invention.
- FIG. 1 is a schematic cross-sectional view showing an example of an embodiment of a film with a precursor layer to be plated according to the present invention.
- the configuration having the undercoat layer 15 and the plated layer precursor layer 30 only on one side of the substrate 12 is shown.
- the film with the plated layer precursor layer of the present invention is of course on both sides of the substrate 12.
- the structure which has the undercoat layer 15 and the to-be-plated layer precursor layer 30 may be sufficient.
- substrate, undercoat layer, and to-be-plated layer precursor layer which comprise the film with a to-be-plated layer precursor layer of this invention are explained in full detail.
- the type of the substrate is not particularly limited as long as it has two main surfaces and supports a patterned plating layer to be described later.
- an insulating substrate is preferable, and more specifically, a resin substrate, a ceramic substrate, a glass substrate, and the like can be given.
- the resin substrate material include polyethersulfone resin, poly (meth) acrylic resin, polyurethane resin, polyester resin (for example, polyethylene terephthalate or polyethylene naphthalate), polycarbonate resin, and polysulfone resin.
- examples thereof include resins, polyamide resins, polyarylate resins, polyolefin resins, cellulose resins, polyvinyl chloride resins, and cycloolefin resins.
- polyester resins for example, polyethylene terephthalate or polyethylene naphthalate
- polyolefin resins are preferable.
- the poly (meth) acrylic resin means a polyacrylic resin or a polymethacrylic resin.
- the thickness (mm) of the substrate is not particularly limited, but is preferably from 0.01 to 2 mm, more preferably from 0.02 to 0.1 mm, from the viewpoint of balance between handleability and thinning.
- the substrate preferably transmits light appropriately. Specifically, the total light transmittance of the substrate is preferably 85 to 100%.
- the substrate may have a multilayer structure, and for example, a functional film may be included as one layer.
- the substrate itself may be a functional film.
- a functional film For polarizing plates, retardation films, cover plastics, hard coat films, barrier films, adhesive films, electromagnetic wave shielding films, heating films, antenna films, and devices other than touch panels A wiring film etc. are mentioned.
- Specific examples of functional films used for liquid crystal cells particularly related to touch panels include NPF series (manufactured by Nitto Denko) or HLC2 series (manufactured by Sanlitz) as polarizing plates, and WV film (Fuji Film) as retardation films.
- Cover plastics such as FAINDE (manufactured by Dainippon Printing), Technoloy (manufactured by Sumitomo Chemical), Iupilon (manufactured by Mitsubishi Gas Chemicals), Sylplus (manufactured by NS
- the hard coat film such as Showa Denko include H series (Lintec), FHC series (Higashiyama Film) or KB film (KIMOTO). These may form a pattern-like to-be-plated layer on the surface of each functional film.
- cellulose triacetate may be used as described in JP-A-2007-26426.
- cellulose triacetate can be used instead of cycloolefin (co) polymer, and examples thereof include ZEONOR (manufactured by ZEON Corporation).
- the thickness of the undercoat layer is not particularly limited, but is generally preferably 0.01 to 100 ⁇ m, more preferably 0.05 to 20 ⁇ m, and still more preferably 0.05 to 10 ⁇ m.
- the surface hardness of the undercoat layer is 10 N / mm 2 or less, preferably 8N / mm 2 or less, more preferably 5N / mm 2 or less.
- the surface hardness of an undercoat layer can be calculated
- the undercoat layer has a friction coefficient with the release paper of 5 or less, preferably 3 or less, and more preferably 1 or less. Note that the coefficient of friction of the undercoat layer with the release paper can be determined by the method described above. By setting the surface hardness of the undercoat layer and the coefficient of friction with the release paper within the above numerical range, a metal layer having excellent roll-to-roll manufacturability and excellent adhesion to the substrate is formed. The film with a to-be-plated layer precursor layer which can be obtained is obtained.
- the material of the undercoat layer is not particularly limited as long as the surface hardness and the coefficient of friction with the release paper are within a predetermined range, but preferably includes a urethane resin.
- the urethane resin include a reaction product of a diol compound and a diisocyanate compound.
- the diol compound include ethylene glycol, propylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentane.
- alkylene oxide adduct (For example, ethylene oxide adduct, propylene oxide adduct, etc.) of these compounds is mentioned.
- polyalkylene glycol is preferable, and polyethylene glycol, polypropylene glycol, or polytetramethylene glycol is more preferable from the viewpoint of easily adjusting the surface hardness and the coefficient of friction with the release paper within a predetermined range.
- the average added mole number of oxyalkylene in the polyalkylene glycol is preferably 3-20.
- the weight average molecular weight of the polyalkylene glycol is preferably 100 to 2000.
- a diol compound may be used individually by 1 type, and 2 or more types may be mixed and used for it.
- diisocyanate compound examples include 2,4-tolylene diisocyanate, dimer of 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, p-xylylene diisocyanate, m-xylylene diisocyanate, 4,4 Aromatic diisocyanate compounds such as' -diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, or 3,3'-dimethylbiphenyl-4,4'-diisocyanate; hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, Or aliphatic diisocyanate compounds such as dimer acid diisocyanate; isophorone diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), methylcyclohexane-2, 4 (or 2,6) diisocyanate, or alicyclic diis
- aliphatic diisocyanate compounds such as isophorone diisocyanate and hexamethane diisocyanate are preferable in that the cured product has high transparency.
- a diisocyanate compound may be used individually by 1 type, and 2 or more types may be mixed and used for it.
- the urethane resin is synthesized, for example, by adding the known diisocyanate compound and diol compound to an aprotic solvent with a known catalyst and heating.
- aprotic solvent with a known catalyst and heating.
- combination According to the objective, it can select suitably, and 1: 1.2-1.2: 1 are preferable.
- a photocurable material may be used as the urethane resin.
- the photocurable urethane resin it is preferable to use a urethane (meth) acrylate synthesized from a diisocyanate compound, a diol compound, and a hydroxyalkyl (meth) acrylate.
- urethane di (meth) acrylate is preferable from the viewpoint of easily adjusting the surface hardness and the coefficient of friction with the release paper within a predetermined range, and particularly a urethane di (meth) acrylate oligomer having a weight average molecular weight range described later.
- (meth) acrylate means an acrylate or a methacrylate.
- a diisocyanate compound and a diol compound Moreover, a preferable aspect is also the same.
- hydroxyalkyl (meth) acrylate examples include hydroxyethyl (meth) acrylate (for example, 2-hydroxyethyl (meth) acrylate), hydroxypropyl (meth) acrylate (for example, 2-hydroxypropyl (meth) acrylate), hydroxy Butyl (meth) acrylate (eg 2-hydroxybutyl (meth) acrylate), hydroxybutyl (meth) acrylate (eg 4-hydroxybutyl (meth) acrylate), hydroxyhexyl (meth) acrylate (eg 6-hydroxyhexyl) (Meth) acrylates) or hydroxyl group-containing (meth) acrylates such as pentaerythritol tri (meth) acrylate; caprolactone modified products or alkyl oxide modified products thereof Representative hydroxyl group-containing (meth) acrylate modified product; addition reaction product of monoepoxy compound such as butyl glycidyl ether, 2-ethyl
- hydroxyethyl (meth) acrylate or hydroxybutyl (meth) acrylate is preferable from the viewpoint of easily adjusting the surface hardness and the coefficient of friction with the release paper within a predetermined range.
- a hydroxyalkyl (meth) acrylate may be used individually by 1 type, and 2 or more types may be mixed and used for it.
- the reactive dilution monomer include alicyclic (meth) acrylates such as isobornyl (meth) acrylate and cyclohexyl (meth) acrylate; or aromatic (meth) acrylates such as phenoxyethyl (meth) acrylate. It is done.
- 1 type may be used independently and 2 or more types may be mixed and used for it.
- Urethane (meth) acrylate can be produced by a known method. For example, after adding a diol compound to a diisocyanate compound and reacting at 50 to 80 ° C. for about 3 to 10 hours, hydroxyalkyl (meth) acrylate and any reaction dilution monomer, a catalyst such as dibutyltin dilaurate, and methylhydroquinone It is possible to synthesize by adding a polymerization inhibitor such as the above and further reacting at 60 to 70 ° C. for about 3 to 12 hours.
- a catalyst such as dibutyltin dilaurate, and methylhydroquinone
- the use ratio of the diisocyanate compound, the diol compound and the hydroxyalkyl (meth) acrylate is not particularly limited as long as the desired surface hardness and the coefficient of friction with the release paper are obtained, but 0.9 ⁇ (total number of isocyanate groups of the diisocyanate compound) / (Total number of hydroxyl groups of diol compound and hydroxyalkyl (meth) acrylate) is preferably ⁇ 1.1.
- the weight average molecular weight of the urethane (meth) acrylate is 5,000 or more and 120,000 as a polystyrene conversion value by GPC (gel permeation chromatography) method from the viewpoint that the surface hardness and the coefficient of friction with the release paper are easily set within a predetermined range. Or less, more preferably 15,000 or more and 80,000 or less, and further preferably 30,000 or more and 70,000 or less.
- the GPC method uses HLC-8020GPC (manufactured by Tosoh Corporation), TSKgel SuperHZM-H, TSKgel SuperHZ4000, TSKgel SuperHZ2000 (manufactured by Tosoh Corporation, 4.6 mm ID ⁇ 15 cm) as columns and THF (tetrahydrofuran) as an eluent. ).
- the undercoat layer contains other additives (for example, sensitizers, antioxidants, antistatic agents, ultraviolet absorbers, fillers, particles, flame retardants, surfactants, lubricants, plasticizers, etc.) It may be.
- additives for example, sensitizers, antioxidants, antistatic agents, ultraviolet absorbers, fillers, particles, flame retardants, surfactants, lubricants, plasticizers, etc.
- the method for forming the undercoat layer on the substrate is not particularly limited.
- a method of transferring to the substrate surface transfer method.
- the coating method is preferable from the viewpoint of easy control of the thickness.
- the aspect of the coating method will be described in detail.
- the composition used in the coating method preferably contains at least various additives in addition to the urethane resin described above.
- a urethane resin contains a polymerizable group (for example, ethylenically unsaturated group etc.) in the structure
- a composition contains a polymerization initiator.
- the content of the polymerization initiator is not particularly limited, but is preferably 0.01 to 5% by mass with respect to the total mass of the composition in terms of curability of the undercoat layer. More preferably, it is 3% by mass.
- a polymerization initiator what is illustrated in description of the to-be-plated layer precursor layer mentioned later can be used.
- a solvent is contained in a composition from the point 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, or propylene glycol monomethyl ether; acids such as acetic acid; acetone, Ketone solvents such as methyl ethyl ketone or cyclohexanone; amide solvents such as formamide, dimethylacetamide or N-methylpyrrolidone; nitrile solvents such as acetonitrile or propionitrile; ester solvents such as methyl acetate or ethyl acetate; Carbonate solvents such as dimethyl carbonate or diethyl carbonate; besides these, ether solvents, glycol solvents, amine solvents, thiol solvents, halogen solvents and the like can be mentioned.
- alcohol solvents amide solvents, ketone solvents, nitrile solvents, or carbonate solvents are preferable.
- the content of the solvent in the composition is not particularly limited, but is preferably 50 to 98% by mass, more preferably 60 to 95% by mass with respect to the total amount of the composition. Within the above range, the composition is easy to handle and the layer thickness is easily controlled.
- the method for coating the composition on the substrate is not particularly limited, and a known method (for example, a spin coating method, a die coating method, a dip coating method, or the like) can be used.
- a known method for example, a spin coating method, a die coating method, a dip coating method, or the like
- substrate you may apply
- an embodiment is preferred in which the composition is applied onto 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 coating film of an undercoat layer is formed with the urethane resin containing a polymeric group, it is preferable to perform exposure.
- the method to expose is not specifically limited, For example, the method of irradiating actinic light or a radiation is mentioned.
- actinic light UV (ultraviolet) lamps, 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.
- the polymeric group contained in the compound in a coating film is activated, the bridge
- the exposure energy long 10 ⁇ 8000mJ / cm 2 approximately, and preferably from 50 ⁇ 3000mJ / cm 2.
- the to-be-plated layer precursor layer is a layer that is cured in a pattern by exposure to be described later to become a patterned to-be-plated layer, and preferably includes at least a polymerization initiator and the following compound X or composition Y. . More specifically, the to-be-plated layer precursor layer may be a layer containing a polymerization initiator and compound X, or a layer containing a polymerization initiator and composition Y.
- Compound X a functional group that interacts with the plating catalyst or its precursor (hereinafter, also simply referred to as “interactive group”) and a polymerizable group
- Composition Y interaction with the plating catalyst or its precursor
- Polymerization initiator There is no restriction
- examples of polymerization initiators include benzophenones, acetophenones, ⁇ -aminoalkylphenones, benzoins, ketones, thioxanthones, benzyls, benzyl ketals, oxime esters, anthrones, tetramethylthiuram monosulfide Bisacylphosphinoxides, acylphosphine oxides, anthraquinones, azo compounds, etc., or derivatives thereof.
- the content of the polymerization initiator in the plating layer precursor layer is not particularly limited, but is 0.01 to 5% by mass with respect to the total mass of the plating layer precursor layer in terms of curability of the plating layer. Preferably, it is 0.1 to 3% by mass.
- Compound X is a compound having an interactive group and a polymerizable group.
- the interactive group is intended to be a functional group capable of interacting with a plating catalyst or a precursor thereof applied to the patterned layer to be plated.
- a functional group capable of forming an electrostatic interaction with the plating catalyst or a precursor thereof.
- a nitrogen-containing functional group, a sulfur-containing functional group, an oxygen-containing functional group, or the like that can form a coordination group with a plating catalyst or a precursor thereof can be used.
- ionic polar groups such as carboxylic acid groups, sulfonic acid groups, phosphoric acid groups, and boronic acid groups, ether groups, or A cyano group is preferable, and a carboxylic acid group (carboxyl group) or a cyano group is more preferable.
- Compound X may contain two or more interactive groups.
- 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, and maleic acid ester groups.
- unsaturated carboxylic acid ester groups such as styryl 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 more preferable.
- compound X two or more polymerizable groups may be contained. Further, the number of polymerizable groups contained in the compound X is not particularly limited, and may be one or two or more.
- the compound X 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 more preferably 20000 or more.
- a 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 No. 2009-280905) is used.
- 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).
- a repeating unit having a polymerizable group represented by the following formula (a) hereinafter also referred to as a polymerizable group unit as appropriate
- 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, or a butyl group) Group).
- a substituent for example, a methyl group, an ethyl group, a propyl group, or a butyl group
- 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, or a propylene group), a substituted or unsubstituted group.
- Substituted divalent aromatic hydrocarbon group preferably having 6 to 12 carbon atoms, eg, phenylene group
- R: alkyl group preferably having 6 to 12 carbon atoms, eg, phenylene group
- a single bond, an ester group (—COO—), an amide group (—CONH—), an 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 represents 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 metal layer is more excellent. Group), and those having a total carbon number of 1 to 9 are more preferable.
- 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 metal layer. preferable. Among these, L 2 is more preferably a single bond or a total carbon number of 1 to 15.
- the divalent organic group is 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 or polymerizability) 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 or an ether group is 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 polymer is easily synthesized and the adhesion of the metal layer 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 terms of easy polymer synthesis and better adhesion of the metal layer. 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 or 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) Groups 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 repeating units in the polymer from the viewpoint of reactivity (curability or polymerization) 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 still more preferable.
- polymers described in paragraphs [0106] to [0112] of JP2009-007540A and the paragraphs [0065] to [0070] of JP2006-135271A.
- 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).
- 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, or 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 An oxy group, an alkyleneoxycarbonyl group, an 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.
- Q represents an n-valent linking group
- R a represents a hydrogen atom or a methyl group
- n represents an integer of 2 or more.
- R a represents a hydrogen atom or a methyl group, preferably a hydrogen atom.
- the valence n of Q is 2 or more, preferably 2 or more and 6 or less, more preferably 2 or more and 5 or less, more preferably 2 or more from the viewpoint of further improving the adhesion between the substrate and the metal layer. More preferably, it is 4 or less.
- Examples of the n-valent linking group represented by Q include a group represented by the formula (1A), a group represented by the formula (1B),
- composition Y is a composition containing a compound having an interactive group and a compound having a polymerizable group. That is, the to-be-plated layer precursor layer includes two types of compounds, that is, a compound having an interactive group and a compound having a polymerizable group.
- the definitions of the interactive group and the polymerizable group are as described above.
- the definition of the interactive group contained in the compound having an 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.
- a polymeric group is not contained in the compound which has an interactive group.
- the compound having a polymerizable group is a so-called monomer, and is preferably a polyfunctional monomer having two or more polymerizable groups from the viewpoint that the hardness of the formed pattern-like plated layer is more excellent.
- a monomer having 2 to 6 polymerizable groups is preferable to use as the polyfunctional monomer.
- the molecular weight of the polyfunctional monomer used is preferably 150 to 1000, more preferably 200 to 700.
- the distance (distance) between a plurality of polymerizable groups is preferably from 1 to 15 in terms of the number of atoms, and more preferably from 6 to 10.
- the compound having a polymerizable group may contain an interactive group.
- the mass ratio of the compound having an interactive group and the compound having a polymerizable group is not particularly limited. From the viewpoint of the balance between the strength of the layer to be plated and the plating suitability, 0.1 to 10 is preferable, and 0.5 to 5 is more preferable.
- the content of compound X (or composition Y) in the plating layer precursor layer is not particularly limited, but is preferably 50% by mass or more, and 80% by mass or more with respect to the total mass of the plating layer precursor layer. More preferred.
- the upper limit is not particularly limited, but is preferably 99.5% by mass or less.
- components other than the polymerization initiator and the compound X or the composition Y may be contained.
- a monomer (however, excluding the compound represented by the above formula (1)) may be included in the plating layer precursor layer.
- the monomer By including the monomer, the crosslinking density and the like in the patterned layer to be plated can be appropriately controlled.
- the monomer to be used is not particularly limited.
- the compound having addition polymerization property includes a compound having an ethylenically unsaturated bond
- the compound having ring-opening polymerization property includes a compound having an epoxy group. It is done.
- 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 method for forming the plated layer precursor layer on the surface of the undercoat layer on the substrate is not particularly limited, and the composition containing various components described above is applied to the surface of the undercoat layer on the substrate to be plated.
- Examples thereof include a method of forming a precursor layer (coating method), a method of forming a plated layer precursor layer on a temporary substrate, and transferring it to the surface of the undercoat layer on the substrate (transfer method).
- the coating method is preferable from the viewpoint of easy control of the thickness.
- the aspect of the coating method will be described in detail.
- the composition used in the coating method includes at least the polymerization initiator and the compound X or the composition Y described above.
- the other component mentioned above may be contained as needed.
- a solvent is contained in a composition from the point of handleability.
- the solvent which can be used is not specifically limited, For example, the solvent used at the time of formation of the undercoat layer mentioned above can be used.
- the content of the solvent in the composition is not particularly limited, but is preferably 50 to 98% by mass and more preferably 70 to 95% by mass with respect to the total amount of the composition. Within the above range, the composition is easy to handle and the layer thickness is easily controlled.
- the method for coating the composition on the substrate is not particularly limited, and a known method (for example, a spin coating method, a die coating method, a dip coating method, or the like) can be used.
- a known method for example, a spin coating method, a die coating method, a dip coating method, or the like
- substrate you may apply
- 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 thickness of the precursor layer to be plated is not particularly limited, but is preferably 0.01 to 20 ⁇ m, more preferably 0.1 to 10 ⁇ m, and still more preferably 0.1 to 5 ⁇ m.
- FIG. 2 is a schematic cross-sectional view showing an example of an embodiment of the conductive film of the present invention.
- the conductive film of the present invention will be described with reference to the drawings, taking the method for producing the conductive film 100 as an example. Moreover, the manufacturing method of the film with a to-be-plated layer precursor layer of this invention and the manufacturing method of the film with a pattern-like to-be-plated layer of this invention are also demonstrated collectively. In addition, embodiment of this invention is not restricted to the aspect shown below.
- the conductive film of the present invention can be produced by a production method having the following step 1, step 2 and step 3.
- Step 1 On the substrate, an undercoat layer is formed from the substrate side, and a to-be-plated layer precursor layer is formed on the undercoat layer.
- Step 2 Forming a patterned plated layer by subjecting the plated layer precursor layer to pattern exposure and curing in a pattern, a film forming step with a patterned plated layer,
- Process 3 Metal layer formation process (conductive film formation process) which forms a metal layer on a pattern-like to-be-plated layer by plating process
- Step 1 is a step of forming a film with a precursor layer to be plated by laminating an undercoat layer and a precursor layer to be plated on the substrate in this order from the substrate side. That is, it is a process of forming the film 10 with a to-be-plated layer precursor layer as shown in FIG.
- step 1 first, an undercoat layer 15 is formed on the substrate 12, and a to-be-plated layer precursor layer (unexposed coating film) 30 is disposed on the undercoat layer 15.
- the undercoat layer 15 is formed, for example, by forming a coating film on the substrate 12 by the above-described coating method or the like and then curing by exposure or the like as necessary.
- Step 2 is a step of exposing the coating film of the plated layer precursor layer in a pattern to form a patterned plated layer on the substrate. More specifically, as shown in FIG. 3A, a pattern as shown by a black arrow through a photomask 25 with respect to the plating layer precursor layer 30 constituting the film with a plating layer precursor layer 10. It is a step (FIG. 3B) in which the reaction of the polymerizable group is accelerated by exposure to cure, and then the unexposed area is removed to obtain the patterned plated layer 20.
- the patterned plated layer 20 of the film 50 with the patterned plated layer formed by the above process adsorbs (attaches) the plating catalyst or its precursor in the process 3 described later according to the function of the interactive group. . That is, the patterned plated layer 20 functions as a good receiving layer for the plating catalyst or its precursor. Moreover, a polymeric group is utilized for the coupling
- substrate is not restrict
- the method of irradiating actinic light or a radiation is mentioned.
- the irradiation with actinic light UV (ultraviolet) lamps, 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.
- the coating film on the substrate in a pattern As a specific mode of exposing the coating film on the substrate in a pattern, scanning exposure with an infrared laser, high-illuminance flash exposure such as a xenon discharge lamp using a mask, or infrared lamp exposure using a mask is preferable. It is mentioned in.
- the polymeric group contained in the compound in a coating film is activated, the bridge
- the exposure energy long 10 ⁇ 8000mJ / cm 2 approximately, and preferably from 50 ⁇ 3000mJ / cm 2.
- the unexposed area in the plated layer precursor layer 30 is removed to form the patterned plated layer 20.
- 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 immersion method is preferable.
- 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 a compound to be used is dissolved is used as a developer and immersed in the developer may be used.
- a pattern-form to-be-plated layer is a layer containing the interactive group mentioned above.
- the patterned plating layer is subjected to a plating treatment.
- the thickness of the patterned plating layer formed by the above treatment is not particularly limited, but is preferably 0.01 to 10 ⁇ m, more preferably 0.2 to 5 ⁇ m, and more preferably 0.3 to 1.0 ⁇ m from the viewpoint of productivity. Further preferred.
- the pattern shape of the pattern-like plated layer is not particularly limited, and is adjusted according to a place where a metal layer to be described later is to be formed, and examples thereof include a mesh pattern.
- the length W of one side of the lattice (opening) in the mesh pattern is preferably 800 ⁇ m or less, more preferably 600 ⁇ m or less, preferably 50 ⁇ m or more, and more preferably 400 ⁇ m or more.
- the shape of the lattice is not particularly limited, and may be a substantially rhombus shape or a polygonal shape (for example, a triangle, a quadrangle, or a hexagon). Further, the shape of one side may be a curved shape or a circular arc shape in addition to a linear shape.
- the line width of the patterned plated layer 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 the low resistance of the metal layer disposed on the patterned plated layer. More preferred is 9 ⁇ m or less, and most preferred is 7 ⁇ m or less. On the other hand, the lower limit is preferably 0.5 ⁇ m or more, and more preferably 1.0 ⁇ m or more.
- Step 3 applies a plating catalyst or a precursor thereof to the patterned plating layer formed in Step 2 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 metal layer on the patterned plated layer. As shown in FIG. 3C, by performing this step, the metal layer 22 is disposed on the patterned plated layer 20, and the conductive film 100 is obtained.
- step 3-1 a step of applying a plating catalyst or a precursor thereof to the patterned layer to be plated
- step 3-1 a step of applying a plating catalyst or a precursor thereof to the patterned layer to be plated
- step 3-2 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 3-2).
- Step 3-1 Catalyst application step
- a plating catalyst or a precursor thereof is applied to the patterned layer to be plated.
- the interactive group contained in the pattern-like plated layer described above attaches (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 patterned plating layer and on the surface of the patterned plating layer.
- 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.
- any catalyst can be used as long as it becomes an active nucleus at the time of plating.
- Specific examples include metals having catalytic ability for autocatalytic reduction reaction (known as metals capable of electroless plating having a lower ionization tendency than Ni).
- metals capable of electroless plating having a lower ionization tendency than Ni Specifically, Pd, Ag, Cu, Ni, Pt, Au, Co, etc. are mentioned. Among these, Ag, Pd, Pt, or Cu is particularly preferable because of its high catalytic ability.
- a metal colloid may be used as the plating catalyst.
- the plating catalyst precursor used in this step can be used without particular limitation as long as it can become a plating catalyst by a chemical reaction. Mainly, metal ions of the metals mentioned as the plating catalyst are used.
- the metal ion which is a plating catalyst precursor becomes a zero-valent metal which is a plating catalyst by a reduction reaction.
- the metal ions that are the plating catalyst precursor may be separately changed to a zero-valent metal by a reduction reaction to serve as a plating catalyst.
- the plating catalyst precursor may be immersed in a plating bath and changed to a metal (plating catalyst) by a reducing agent in the plating bath. It is preferable to give a metal ion to a pattern-like to-be-plated layer 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 ) and M 3 / n (PO 4 ) (M represents an n-valent metal atom).
- a metal ion the thing which said metal salt dissociated can be used suitably.
- Specific examples include, for example, Ag ions, Cu ions, Al ions, Ni ions, Co ions, Fe ions, and Pd ions. Among them, those capable of multidentate coordination are preferable, and coordination is possible. From the viewpoint of the number of types of functional groups and catalytic ability, Ag ions or Pd ions are more preferable.
- a metal salt is dissolved in an appropriate solvent, a solution containing dissociated metal ions is prepared, and the solution is applied on the pattern-like layer to be plated.
- substrate with which the pattern-like to-be-plated layer was formed may be immersed in the solution.
- the solvent water or an organic solvent is appropriately used.
- 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 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 to be plated varies depending on the type of plating bath used, the type of catalyst metal, the type of interactive base of the patterned layer to be plated, and the method of use. from the viewpoint of precipitation of, preferably 5 ⁇ 1000mg / m 2, more preferably 10 ⁇ 800mg / m 2, more 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.
- the electroless plating treatment in this step is performed, for example, by rinsing a substrate provided with a patterned plating layer provided with metal ions to remove excess metal ions, and then immersing the substrate in an electroless plating bath.
- a known electroless plating bath can be used. In the electroless plating bath, reduction of metal ions and subsequent electroless plating are performed.
- the reduction of the metal ions in the patterned layer to be plated is performed as a separate process before the electroless plating treatment by preparing a catalyst activation liquid (reducing liquid) separately from the above-described embodiment using the electroless plating liquid. It is also possible.
- the catalyst activation liquid is a liquid in which a reducing agent capable of reducing metal ions to a zero-valent metal is dissolved.
- the concentration of the reducing agent with respect to the whole liquid is preferably 0.1 to 50% by mass, more preferably 1 to 30% by mass.
- the reducing agent it is possible to use a boron-based reducing agent such as sodium borohydride or dimethylamine borane, formaldehyde, hypophosphorous acid and the like. In soaking, it is preferable to soak while stirring or shaking.
- 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 needs to be a solvent that can be used in water, and from this point, ketones such as acetone or alcohols such as methanol, ethanol, and isopropanol are preferable.
- 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 electrolytic plating treatment refers to an operation of depositing a metal by an electric current using a solution in which metal ions to be deposited as a plating are dissolved.
- an electroplating process can be performed as needed after the said electroless-plating process.
- the thickness of the formed patterned metal layer can be adjusted as appropriate.
- a method of electrolytic plating a conventionally known method can be used.
- examples of the metal used for electrolytic plating include copper, chromium, lead, nickel, gold, silver, tin, and zinc. From the viewpoint of conductivity, copper, gold, or silver is preferable. Is more preferable.
- the film thickness of the metal layer obtained by electrolytic plating can be controlled by adjusting the metal concentration contained in the plating bath, the current density, or the like.
- the thickness of the metal layer formed by the above procedure is not particularly limited, and an optimum thickness is appropriately selected according to the purpose of use. From the viewpoint of conductive properties, it is preferably 0.1 ⁇ m or more, and 0.5 ⁇ m or more. More preferably, the thickness is 1 to 30 ⁇ m.
- the type of metal constituting the metal layer is not particularly limited, and examples thereof include copper, chromium, lead, nickel, gold, silver, tin, and zinc. From the viewpoint of conductivity, copper, gold, Or silver is preferable and copper or silver is more preferable.
- the pattern shape of the metal layer is not particularly limited.
- the metal layer is adjusted according to the pattern shape of the patterned plated layer, and examples thereof include a mesh pattern.
- the metal layer of the mesh pattern can be suitably applied as a sensor electrode in the touch panel.
- the range of the length W of one side of the lattice (opening) in the mesh pattern, the preferred form of the lattice shape, and the line width of the metal layer are determined by the above-described pattern-shaped covering. This is the same as the aspect of the plating layer.
- the conductive film having a metal layer obtained by the above-described treatment can be applied to various applications, such as a touch panel (or touch panel sensor), a semiconductor chip, various electric wiring boards, FPC (Flexible printed circuits), COF (Chip on Film). ), TAB (Tape Automated Bonding), antenna, multilayer wiring board, and mother board.
- a touch panel sensor capactance type touch panel sensor
- the metal layer in the conductive film functions as a detection electrode or a lead wiring in the touch panel sensor.
- a touch panel sensor for example, a liquid crystal display device, an organic EL (electroluminescence) display device
- a touch panel a so-called capacitive touch panel is preferably exemplified.
- composition for forming layer to be plated Preparation of composition for forming layer to be plated
- the following components were mixed to obtain a composition for forming a layer to be plated.
- MT1007 manufactured by Nippon Paint Co., Ltd.
- a roll-like PET (polyethylene terephthalate) film (trade name “A4300”, manufactured by Toyobo Co., Ltd.) having a thickness of 50 ⁇ m so that the film thickness after drying becomes 2 ⁇ m.
- this was further dried at 80 ° C. for 1 minute to form a coating film.
- the undercoat layer 1 was formed by irradiating and hardening the said coating film with the exposure amount of 0.5 J / cm ⁇ 2 > using the metal halide UV (ultraviolet) lamp.
- the film having the undercoat layer 1 and the laminate film is unwound from one side of the PET film produced as described above, and the opposite surface of the PET film (that is, the surface on which the undercoat layer 1 and the laminate film are not disposed).
- MT1007 manufactured by Nippon Paint Co., Ltd.
- the undercoat layer 2 was formed by irradiating and hardening the said coating film with the exposure amount of 0.5 J / cm ⁇ 2 > using the metal halide UV lamp.
- the film on which the precursor layer 2 to be plated is formed is fed from the roll while peeling the laminate film, and the composition for forming the plating layer is formed on the surface from which the laminate film is peeled (that is, the surface of the undercoat layer 1).
- the composition for forming the plating layer is formed on the surface from which the laminate film is peeled (that is, the surface of the undercoat layer 1).
- the film thickness after drying was 0.6 ⁇ m, and further dried at 80 ° C. for 1 minute to form a coating film of the precursor layer 1 to be plated.
- this was wound around a roll to obtain a film R-1 with a layer precursor layer to be plated.
- the film to be plated precursor layer R-1 is produced by the roll-to-roll, there are also rollers that come into contact with the undercoat layers 1 and 2 on the PET film during the transportation of the PET film.
- the produced film R-1 with a layer to be plated precursor layer was cut into 150 mm square.
- the plated layer precursor layer 2 of the cut film to be plated precursor layer R-1 was irradiated with 1 J / cm 2 using a high-pressure mercury lamp through a 150 mm square mask provided with a conductive pattern. .
- 40 ° C. water was sprayed in the form of a shower for 2 minutes and developed into a pattern, thereby obtaining a film R2-1 with a patterned layer to be plated.
- the obtained film R2-1 with a patterned layer to be plated was added to a Pd ion-imparting solution obtained by diluting only the “MAT-A solution” of the Pd catalyst-imparting solution “MAT” manufactured by Uemura Kogyo Co., Ltd. four times.
- the film R2-1 with a patterned layer to be plated was washed after immersion for 1 minute.
- the obtained film R2-1 with a patterned layer to be plated was immersed in a Pd reducing agent “MAB” of Uemura Kogyo for 5 minutes.
- the film R2-1 with the patterned layer to be plated after immersion is immersed in a plating solution “PEA” manufactured by Uemura Kogyo Co., Ltd. for 5 minutes to deposit copper in a pattern on the layer to be plated.
- Film R3-1 was obtained.
- HNBR hydrogenated nitrile rubber
- Zetpole0020 manufactured by Nippon Zeon
- cyclohexanone cyclohexanone on one side of a roll-like PET (polyethylene terephthalate) film (trade name “A4300”, manufactured by Toyobo Co., Ltd.).
- the applied composition was applied so that the film thickness after drying was 2 ⁇ m, and then further dried at 80 ° C. for 1 minute to form a coating film.
- the undercoat layer 1 was formed by irradiating and hardening the said coating film with the exposure amount of 0.5 J / cm ⁇ 2 > using the metal halide UV (ultraviolet) lamp.
- Example 1 Based on the composition ratios shown in Table 1, polyethylene glycol (PEG Mw (weight average molecular weight): 400 manufactured by Tokyo Chemical Industry Co., Ltd.) and ethoxylated isopropylidenediphenol (bisphenol A) as the diol compound (in the table, “diol component”) -EO addition Aldrich) and isophorone diisocyanate (IPDI Wako Pure Chemical Industries) as a diisocyanate compound (in the table, "diisocyanate component”) were dissolved in methyl ethyl ketone and stirred at 60 ° C for 5 hours.
- PEG Mw weight average molecular weight
- bisphenol A bisphenol A
- IPDI Wako Pure Chemical Industries isophorone diisocyanate
- the obtained composition was further mixed with hydroxybutyl acrylate (HBA manufactured by Tokyo Chemical Industry Co., Ltd.) as a crosslinking component based on the composition ratio shown in Table 1, and dibutyltin dilaurate (mass ratio of 0.1% with respect to the solid component) as a catalyst. Wako Pure Chemical Industries, Ltd.) was added, and the mixture was further stirred for 5 hours. Irgacure 2959 (mass ratio 1% with respect to solid component, manufactured by BASF) was added to the resulting polymerized product, and polydimethylsiloxane (weight average molecular weight 770, mass ratio with respect to solid component 0.1%, Alfa Aesar) was added as an initiator. The undercoat material 1 was obtained.
- HBA hydroxybutyl acrylate
- dibutyltin dilaurate mass ratio of 0.1% with respect to the solid component
- Irgacure 2959 mass ratio 1% with respect to solid component, manufactured by BASF
- Table 1 summarizes the composition of the undercoat material 1.
- a solvent is added so that the composition total mass of the undercoat material 1 may be 100 mass parts, and also the mixing ratio (mass ratio) of methyl ethyl ketone and PGMEA (propyleneglycol monomethyl ether acetate) will be 7: 3.
- the mixing ratio mass ratio of methyl ethyl ketone and PGMEA (propyleneglycol monomethyl ether acetate)
- Undercoat material 2 was prepared in the same manner as undercoat material 1 except that the components shown in Table 1 were used.
- an undercoat layer 1 and an undercoat layer 2 (each having a thickness after drying of 2 ⁇ m) were prepared by the same method as in Comparative Example 1 with a plated layer precursor layer.
- Film T-2 was produced.
- a film T2-2 with a patterned layer to be plated and a conductive film T3-2 were obtained in the same manner as in Comparative Example 1.
- Undercoat material 3 was prepared in the same manner as undercoat material 1 except that the components shown in Table 1 were used.
- an undercoat layer 1 and an undercoat layer 2 (each having a film thickness after drying of 2 ⁇ m) were prepared by the same method as in Comparative Example 1 with a plated layer precursor layer.
- Film T-3 was produced. Further, a film T2-3 with a patterned layer to be plated and a conductive film T3-3 were obtained in the same manner as in Comparative Example 1.
- Undercoat material 4 was prepared in the same manner as undercoat material 1 except that the components listed in Table 1 were used. Moreover, with the undercoat material 4, the undercoat layer 1 and the undercoat layer 2 (each having a thickness after drying of 2 ⁇ m) were prepared by the same method as in Comparative Example 1 with a precursor layer to be plated. Film T-4 was produced. Further, a film T2-4 with a patterned layer to be plated and a conductive film T3-4 were obtained in the same manner as in Comparative Example 1.
- Undercoat material 5 was prepared in the same manner as undercoat material 1 except that the components listed in Table 1 were used.
- an undercoat layer 1 and an undercoat layer 2 (each having a film thickness after drying of 2 ⁇ m) were prepared by the same method as in Comparative Example 1 with a plated layer precursor layer.
- Film T-5 was produced. Further, a film T2-5 with a patterned layer to be plated and a conductive film T3-5 were obtained in the same manner as in Comparative Example 1.
- Undercoat material 6 was prepared in the same manner as undercoat material 1 except that the components listed in Table 1 were used.
- the undercoat layer 1 and the undercoat layer 2 (each having a thickness of 2 ⁇ m after drying) were prepared in the same manner as in Comparative Example 1 with a precursor layer to be plated.
- Film T-6 was produced. Further, a film T2-6 with a patterned layer to be plated and a conductive film T3-6 were obtained in the same manner as in Comparative Example 1.
- Undercoat material 7 was prepared in the same manner as undercoat material 1 except that the components shown in Table 1 were used.
- the undercoat layer 1 and the undercoat layer 2 (each having a thickness of 2 ⁇ m after drying) were prepared in the same manner as in Comparative Example 1 with the plated layer precursor layer.
- Film T-7 was produced. Further, a film T2-7 with a patterned layer to be plated and a conductive film T3-7 were obtained in the same manner as in Comparative Example 1.
- Undercoat material 8 was prepared in the same manner as undercoat material 1 except that the components shown in Table 1 were used. Moreover, with the undercoat material 1 and the undercoat layer 2 (each film thickness after drying is 2 ⁇ m) using the undercoat material 8, a precursor layer to be plated is attached by the same method as in Comparative Example 1. Film R-3 was produced. Further, a film R2-3 with a patterned layer to be plated and a conductive film R3-3 were obtained in the same manner as in Comparative Example 1.
- Undercoat material 9 was prepared in the same manner as undercoat material 1 except that the components shown in Table 1 were used.
- the undercoat layer 1 and the undercoat layer 2 (each having a dried film thickness of 2 ⁇ m) were prepared in the same manner as in Comparative Example 1 with the plated layer precursor layer.
- Film R-4 was produced. Further, a film R2-4 with a patterned layer to be plated and a conductive film R3-4 were obtained in the same manner as in Comparative Example 1.
- Comparative Example 5 An undercoat material 10 was prepared in the same manner as the undercoat material 1 except that the components shown in Table 1 were used. In addition, with the undercoat material 10, the undercoat layer 1 and the undercoat layer 2 (each having a thickness of 2 ⁇ m after drying) were prepared in the same manner as in Comparative Example 1 with the precursor layer to be plated. Film R-5 was produced. Further, a film R2-5 with a patterned layer to be plated and a conductive film R3-5 were obtained in the same manner as in Comparative Example 1.
- Undercoat material 11 was prepared in the same manner as undercoat material 1 except that the components shown in Table 1 were used.
- the undercoat layer 1 and the undercoat layer 2 were prepared by the same method as in Comparative Example 1 with the plated layer precursor layer.
- Film R-6 was produced. Further, a film R2-6 with a patterned layer to be plated and a conductive film R3-6 were obtained in the same manner as in Comparative Example 1.
- Table 1 is shown below.
- the blending amount of each component is based on “part by mass”.
- the solvent was added so that the composition total mass of the undercoat material 1 might be 100 mass parts, and also the mixing ratio (mass ratio) of methyl ethyl ketone and PGMEA was prepared to be 7: 3.
- each urethane (meth) acrylate of the undercoat materials 1 to 7 had a weight average molecular weight in the range of 30,000 to 70,000.
- Diol component Polyethylene glycol (PEG Mw: 400, manufactured by Tokyo Chemical Industry Co., Ltd.) Polyethylene glycol (PEG Mw: 1000 manufactured by Tokyo Chemical Industry Co., Ltd.) Polytetramethylene oxide (PTMO Mw: 650 manufactured by Wako Pure Chemical Industries, Ltd.) Ethoxylated isopropylidene diphenol (Bisphenol A-EO addition Aldrich)
- Diisocyanate component Isophorone diisocyanate Isophorone diisocyanate (IPDI Wako Pure Chemical Industries, Ltd.) Hexamethylene diisocyanate (HDI manufactured by Tokyo Chemical Industry Co., Ltd.)
- Crosslinking component Hydroxyethyl acrylate (HEA Tokyo Chemical Industry Co., Ltd.) Hydroxybutyl acrylate (HBA manufactured by Tokyo Chemical Industry Co., Ltd.) Dipentaerythritol hexaacrylate (DPHA Aldrich)
- Hardness evaluation was implemented with respect to the board
- Friction coefficient evaluation was performed on the substrate on which the undercoat layer 1 was formed. Specifically, firstly, a release paper, Therapy 38BKE (manufactured by Toray Industries, Inc.) was placed without applying force so that the release surface was in contact with the surface of the undercoat layer 1. Next, the load applied when the therapy was moved in the horizontal direction at a speed of 100 mm / min with a 100 g weight placed thereon was measured using a force gauge FGX-2 (manufactured by Nidec Symposium). The coefficient of friction was obtained by dividing the measured value (load) by the weight of the weight. The results are shown in Table 2.
- Alkali resistance evaluation The prepared film with a layer to be plated was immersed in an aqueous solution of sodium hydroxide at 30 ° C. and pH 13.5 for 15 minutes, and the state of the pattern layer to be plated was observed with an optical microscope to evaluate alkali resistance. .
- the alkali resistance was evaluated according to the following criteria. The results are shown in Table 2. “A”: The state of the patterned plated layer did not change. “B”: Peeling of the patterned plated layer was not observed, but the color changed. “C”: Peeling of the patterned plated layer was observed.
- Adhesion evaluation The adhesive test was carried out by attaching the Nichiban adhesion test tape CT-24 to the patterned metal layer of the produced conductive film and sufficiently adhering it, and then peeling the test tape all at once. The evaluation of adhesion was performed according to the following criteria. The results are shown in Table 2. “A”: No peeling of the metal layer was observed. “B”: Peeling was observed in a range of less than 10% in the area of the pattern. “C”: Peeling was observed in a range of 10% or more in the area of the pattern.
- the films with the precursor layer to be plated of Examples 1 to 7 were all excellent in roll-to-roll productivity. Further, it was confirmed that the patterned plated layer films of Examples 1 to 7 were excellent in alkali resistance. Since a plating solution such as a copper plating solution is highly alkaline, being excellent in alkali resistance means being excellent in resistance to the plating solution. In addition, it was confirmed that the patterned metal layers of the conductive films of Examples 1 to 7 were excellent in adhesion after plating, in other words, excellent adhesion between the metal layer and the substrate.
- the film with the precursor layer to be plated of the comparative example did not satisfy the desired performance.
- a conductive film having the metal layer pattern shape of the conductive films T3-1 to T3-7 prepared above as a wiring pattern for a touch panel was prepared, and it was confirmed whether or not it reacted as a touch panel. Reacted.
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Abstract
Description
例えば、特許文献1には、導電膜の形成方法として、「エポキシ基、アミノ基、ビニル基、メルカプト基、アクリロイルオキシ基、フェニル基、及びシアノ基からなる群から選ばれる少なくとも一つの官能基を有するシランカップリング剤をpH1~8の条件下で加水分解して得られる加水分解物及び/又はその縮合物と、樹脂とを含有するプライマー層形成用組成物を用いて、無機基板上にプライマー層を形成する工程(1)と、上記プライマー層上に、めっき触媒又はその前駆体と相互作用を形成する官能基及び重合性基を有するポリマーを含む層を形成し、その後上記ポリマーを含む層に対してエネルギーを付与して、上記プライマー層上に被めっき層を形成する工程(2)と、上記被めっき層にめっき触媒又はその前駆体を付与する工程(3)と、めっき触媒又はその前駆体が付与された上記被めっき層に対してめっき処理を行い、上記被めっき層上に金属層を形成する工程(4)と、を備える金属層を有する積層体の製造方法。」が記載されている。
また、特許文献1には、金属層の密着性をより向上させる観点から、プライマー層中に含まれる樹脂としてエラストマーを用いることが好ましいことが記載されている。
本発明者らは、特許文献1の如くパターン状被めっき層を用いる方法によりロールtoロールで導電膜を連続的に製造する方法について検討していたところ、上記プライマー層(以下「アンダーコート層」ともいう。)としてエラストマー樹脂を用いた場合には、ロール搬送の際にフィルムがロール表面に引っかかり、搬送できない場合があることを知見するに至った。また、この現象は、特に、エラストマーから形成されたアンダーコート層を基板上に配置したフィルムを、アンダーコート層がロールに接するようにロール搬送した際に生じ易いことを明らかとした。
また、本発明は、導電性フィルム及びタッチパネルを提供することも課題とする。
すなわち、以下の構成により上記目的を達成することができることを見出した。
上記アンダーコート層は、その表面における硬度が10N/mm2以下であり、且つ、離形紙との摩擦係数が5以下である、被めっき層前駆体層付きフィルム。
(2) 上記被めっき層前駆体層が、重合開始剤と、以下の化合物X又は組成物Yとを含む、(1)に記載の被めっき層前駆体層付きフィルム。
化合物X:めっき触媒又はその前駆体と相互作用する官能基、及び、重合性基を有する化合物
組成物Y:めっき触媒又はその前駆体と相互作用する官能基を有する化合物、及び、重合性基を有する化合物を含む組成物
(3) 基板と、上記基板上に配置されたアンダーコート層と、上記アンダーコート層上に配置されたパターン状被めっき層と、を有するパターン状被めっき層付きフィルムであって、
上記アンダーコート層は、その表面における硬度が10N/mm2以下であり、且つ、離形紙との摩擦係数が5以下である、パターン状被めっき層付きフィルム。
(4) (3)に記載のパターン状被めっき層付きフィルムと、上記パターン状被めっき層付きフィルム中の上記パターン状被めっき層上に配置された金属層とを有する、導電性フィルム。
(5) 上記金属層が、無電解めっき処理により形成された、(4)に記載の導電性フィルム。
(6) (4)又は(5)に記載の導電性フィルムを含む、タッチパネル。
更に、本発明によれば、導電性フィルム及びタッチパネルを提供することもできる。
以下に記載する構成要件の説明は、本発明の代表的な実施態様に基づいてなされることがあるが、本発明はそのような実施態様に限定されるものではない。
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及び上限値として含む範囲を意味する。
また、本明細書中における「活性光線」又は「放射線」とは、例えば、水銀灯の輝線スペクトル、エキシマレーザーに代表される遠紫外線、極紫外線(EUV光)、X線、及び、電子線(EB)等を意味する。また、本発明において光とは、活性光線又は放射線を意味する。
また、本明細書中における「露光」とは、特に断らない限り、水銀灯、エキシマレーザーに代表される遠紫外線、極紫外線、X線、及び、EUV光等による露光のみならず、電子線、及び、イオンビーム等の粒子線による描画も露光に含める。
本発明の被めっき層前駆体層付きフィルム基板は、基板と、上記基板上に配置されたアンダーコート層と、上記アンダーコート層上に配置された被めっき層前駆体層と、を有し、
上記アンダーコート層は、その表面における硬度(以下「表面硬度」ともいう。)が10N/mm2以下であり、且つ、離形紙との摩擦係数が5以下である。
(表面硬度)
フィッシャーインスツルメンツ社製HM500型皮膜硬度計を用いて先端曲率半径0.2mmの球状圧子をアンダーコート層(膜厚 2μm)の表面に接触させ、最大荷重2mN、負荷時間10secの条件でユニバーサル硬度(N/mm2)を測定する。
(摩擦係数)
離形紙を、その離形面がアンダーコート層の表面に接するようにして、力をかけずに乗せる。次いで、その上に100gの分銅を乗せて水平方向に100mm/minの速度で離形紙を動かしたときにかかる荷重を、フォースゲージFGX-2(日本電産シンポ社製)を用いて測定する。
摩擦係数は、得られた測定値(荷重)を分銅重さで除すことにより求める。
摩擦係数の評価試験では、「離形紙」としてセラピール38BKE(東レ社製)を用いた。
これは、詳細には明らかではないが、以下のように推測される。
本発明の被めっき層前駆体層付きフィルムの特徴は、アンダーコート層の物性値を、表面硬度が10N/mm2以下、且つ、離形紙との摩擦係数を5以下としている点にある。
本発明者らは、アンダーコート層として特許文献1に記載されるようなエラストマー樹脂を用いたフィルムをロールで搬送し難いことの理由は、上記アンダーコート層がロールと接触した際に変形し、ロールの回転を止めてしまうことにあると推測している。この現象は、特に、エラストマーから形成されたアンダーコート層を基板上に配置したフィルムを、アンダーコート層がロールに接するようにロール搬送した際に生じ易い。また、上記フィルムのアンダーコート層上に更に被めっき層前駆体層を形成したフィルムを被めっき層前駆体層がロールに接するようにロール搬送する際であっても、上記被めっき層前駆体層の膜厚が薄い場合には上記のような搬送不良が生じ易い。これは、被めっき層前駆体層の膜厚が薄い場合は、下層であるアンダーコート層の物性による影響を受けやすいためであると考えられる。
一方で、アンダーコート層は、その上層にパターン状被めっき層を介して金属層が形成される。このため、アンダーコート層をロールとの接触で変形しにくい剛直な材料で形成すると、パターン状被めっき層及び金属層が形成時に生じる応力の緩和がされにくく、パターン状被めっき層とアンダーコート層の界面、及び、パターン状被めっき層と金属層の界面が剥離しやすい傾向にある。つまり、基板上に金属層を良好に密着させることが困難となると考えられる。
本発明者らは、上記知見に基づいて種々の検討を行うことで、アンダーコート層の物性値を、表面硬度が10N/mm2以下、且つ、離形紙との摩擦係数を5以下とした場合に、アンダーコート層がロールと接触しても変形せず、また金属層の密着性にも優れることを明らかとした。
本発明の被めっき層前駆体層付きフィルムは、基板と、上記基板上に配置されたアンダーコート層と、上記アンダーコート層上に配置された被めっき層前駆体層とを有する。
図1は、本発明の被めっき層前駆体層付きフィルムの実施形態の一例を示す断面模式図である。図1の被めっき層前駆体層付きフィルム10は、基板12と、上記基板12上に配置されたアンダーコート層15と、上記アンダーコート層15上に配置された被めっき層前駆体層30と、を有する。
図1では、基板12の片面にのみアンダーコート層15及び被めっき層前駆体層30を有する構成を示したが、本発明の被めっき層前駆体層付きフィルムは、勿論、基板12の両面にアンダーコート層15及び被めっき層前駆体層30を有する構成であってもよい。
以下、本発明の被めっき層前駆体層付きフィルムを構成する基板、アンダーコート層、及び被めっき層前駆体層について詳述する。
基板は、2つの主面を有し、後述するパターン状被めっき層を支持するものであれば、その種類は特に制限されない。基板としては、絶縁基板が好ましく、より具体的には、樹脂基板、セラミック基板、及び、ガラス基板等が挙げられる。
樹脂基板の材料としては、例えば、ポリエーテルスルホン系樹脂、ポリ(メタ)アクリル系樹脂、ポリウレタン系樹脂、ポリエステル系樹脂(例えば、ポリエチレンテレフタレート、又は、ポリエチレンナフタレート等)、ポリカーボネート系樹脂、ポリスルホン系樹脂、ポリアミド系樹脂、ポリアリレート系樹脂、ポリオレフィン系樹脂、セルロース系樹脂、ポリ塩化ビニル系樹脂、及び、シクロオレフィン系樹脂等が挙げられる。なかでも、ポリエステル系樹脂(例えば、ポリエチレンテレフタレート、又は、ポリエチレンナフタレート等)、又は、ポリオレフィン系樹脂が好ましい。なお、ポリ(メタ)アクリル系樹脂とは、ポリアクリル系樹脂又はポリメタクリル樹脂を意味する。
基板の厚み(mm)は特に制限されないが、取り扱い性及び薄型化のバランスの点から、0.01~2mmが好ましく、0.02~0.1mmがより好ましい。
また、基板は、光を適切に透過することが好ましい。具体的には、基板の全光線透過率は、85~100%であることが好ましい。
また、基板は複層構造であってもよく、例えば、その一つの層として機能性フィルムを含んでいてもよい。なお、基板自体が機能性フィルムであってもよい。機能性フィルムの例としては特に限定はされないが、偏光板、位相差フィルム、カバープラスチック、ハードコートフィルム、バリアフィルム、粘着フィルム、電磁波遮蔽フィルム、発熱フィルム、アンテナフィルム、及び、タッチパネル以外のデバイス用配線フィルム等が挙げられる。
特にタッチパネルと関係する液晶セルに用いられる機能性フィルムの具体例として、偏光板としてはNPFシリーズ(日東電工社製)又はHLC2シリーズ(サンリッツ社製)等、位相差フィルムとしてはWVフィルム(富士フイルム社製)等、カバープラスチックとしてはFAINDE(大日本印刷製)、テクノロイ(住友化学製)、ユーピロン(三菱瓦斯化学製)、シルプラス(新日鐵住金製)、ORGA(日本合成化学製)又はSHORAYAL(昭和電工製)等、ハードコートフィルムとしてはHシリーズ(リンテック社製)、FHCシリーズ(東山フィルム社製)又はKBフィルム(KIMOTO社製)等が挙げられる。これらは、各機能性フィルムの表面上にパターン状被めっき層を形成してもよい。
また、偏光板及び位相差フィルムにおいては、特開2007-26426号公報に記載のようにセルローストリアセテートが用いられることがある。なかでも、めっきプロセスに対する耐性の観点から、セルローストリアセテートをシクロオレフィン(コ)ポリマーに変えて使用することもでき、例えばゼオノア(日本ゼオン製)等が挙げられる。
アンダーコート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が更に好ましい。
また、アンダーコート層は、離形紙との摩擦係数が5以下であり、3以下であることが好ましく、1以下であることがより好ましい。なお、アンダーコート層の離形紙との摩擦係数は上述の方法により求めることができる。
アンダーコート層の表面硬度、及び離形紙との摩擦係数を上記の数値範囲とすることで、ロールtoロールでの製造性に優れ、且つ、基板との密着性に優れた金属層を形成することができる被めっき層前駆体層付きフィルムが得られる。
ジオール化合物としては、例えば、エチレングリコール、プロピレングリコール、1,2-プロパンジオール、1,3-プロパンジオール、1,3-ブタンジオール、1,4-ブタンジオール、ネオペンチルグリコール、1,5-ペンタンジオール、1,6-ヘキサンジオール、3-メチルペンタンジオール、ジエチレングリコール、1,4-シクロヘキサンジメタノール、3-メチル-1,5-ペンタンジオール、2-メチル-1,3-プロパンジオール、2,2-ジエチル-1,3-プロパンジオール、2-ブチル-2-エチル-1,3-プロパンジオール、キシリレングリコール、水添ビスフェノールA、又は、ビスフェノールA、ポリアルキレングリコール等のジオール類が挙げられる。また、これらの化合物のアルキレンオキシド付加物(例えば、エチレンオキシド付加物、プロピレンオキシド付加物等)が挙げられる。
これらのなかでも、表面硬度及び離形紙との摩擦係数を所定範囲に調整しやすい観点から、ポリアルキレングリコールが好ましく、ポリエチレングリコール、ポリプロピレングリコール、又は、ポリテトラメチレングリコールがより好ましい。ポリアルキレングリコールにおけるオキシアルキレンの平均付加モル数は、3~20であることが好ましい。また、ポリアルキレングリコールの重量平均分子量は、100~2000であることが好ましい。
ジオール化合物は、1種を単独で用いてもよく2種以上を混合して用いてもよい。
ジイソシアネート化合物は、1種を単独で用いてもよく2種以上を混合して用いてもよい。
なお、(メタ)アクリレートとは、アクリレート又はメタクリレートを意味する。また、ジイソシアネート化合物及びジオール化合物としては、上述したものが挙げられ、また好ましい態様も同じである。
ヒドロキシアルキル(メタ)アクリレートは、1種を単独で用いてもよく2種以上を混合して用いてもよい。
反応性希釈モノマーとしては、例えば、イソボルニル(メタ)アクリレート、シクロヘキシル(メタ)アクリレート等の脂環式(メタ)アクリレート;又は、フェノキシエチル(メタ)アクリレート等の芳香族系(メタ)アクリレート;が挙げられる。
反応性希釈モノマーとしては、1種を単独で用いてもよく2種以上を混合して用いてもよい。
ウレタン(メタ)アクリレートの重量平均分子量は、表面硬度及び離形紙との摩擦係数を所定範囲にしやすい観点から、GPC(ゲル浸透クロマトグラフィー)法によるポリスチレン換算値として、5,000以上120,000以下であることが好ましく、15,000以上80,000以下であることがより好ましく、30,000以上70,000以下であることが更に好ましい。
GPC法は、HLC-8020GPC(東ソー(株)製)を用い、カラムとしてTSKgel SuperHZM-H、TSKgel SuperHZ4000、TSKgel SuperHZ2000(東ソー(株)製、4.6mmID×15cm)を、溶離液としてTHF(テトラヒドロフラン)を用いる方法に基づく。
基板上にアンダーコート層を形成する方法は特に制限されない。例えば、基板上に上述したウレタン樹脂及び任意で添加される各種成分を含んだ組成物を塗布してアンダーコート層を形成する方法(塗布法)、又は、仮基板上にアンダーコート層を形成して、基板表面に転写する方法(転写法)等が挙げられる。なかでも、厚みの制御がしやすい観点からは、塗布法が好ましい。
以下、塗布法の態様について詳述する。
また、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、又はプロピレングリコールモノメチルエーテル等のアルコール系溶剤;酢酸等の酸;アセトン、メチルエチルケトン、又はシクロヘキサノン等のケトン系溶剤;ホルムアミド、ジメチルアセトアミド、又はN-メチルピロリドン等のアミド系溶剤;アセトニトリル、又はプロピオニトリル等のニトリル系溶剤;酢酸メチル、又は酢酸エチル等のエステル系溶剤;ジメチルカーボネート、又はジエチルカーボネート等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、又はハロゲン系溶剤等が挙げられる。
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、又はカーボネート系溶剤が好ましい。
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、60~95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るほか、層厚の制御等がしやすい。
なお、基板の両面にアンダーコート層を配置する場合には、基板の片面ずつに組成物を塗布してもよいし、組成物中に基板を浸漬して基板の両面に一度に塗布してもよい。
取り扱い性及び製造効率の観点からは、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。
被めっき層前駆体層は、後述する露光によってパターン状に硬化されてパターン状被めっき層となる層であり、重合開始剤と、以下の化合物X又は組成物Yと、を少なくとも含むことが好ましい。より具体的には、被めっき層前駆体層は、重合開始剤と化合物Xとを含む層であっても、重合開始剤と組成物Yとを含む層であってもよい。
化合物X:めっき触媒又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)、及び、重合性基を有する化合物
組成物Y:めっき触媒又はその前駆体と相互作用する官能基を有する化合物、及び、重合性基を有する化合物を含む組成物
以下では、まず、被めっき層前駆体層に含まれる材料について詳述する。
重合開始剤としては特に制限はなく、公知の重合開始剤(いわゆる光重合開始剤)等を用いることができる。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、若しくは、アゾ化合物等、又は、それらの誘導体を挙げることができる。
化合物Xは、相互作用性基と重合性基とを有する化合物である。
相互作用性基とは、パターン状被めっき層に付与されるめっき触媒又はその前駆体と相互作用できる官能基を意図し、例えば、めっき触媒又はその前駆体と静電相互作用を形成可能な官能基、又は、めっき触媒又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、若しくは、含酸素官能基等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、及びシアネート基等の含窒素官能基;エーテル基、水酸基、フェノール性水酸基、カルボン酸基、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、及びN-ヒドロキシ構造を含む基等の含酸素官能基;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、、及びスルホン酸エステル構造を含む基等の含硫黄官能基;ホスフォート基、ホスフォロアミド基、ホスフィン基、及び、リン酸エステル構造を含む基等の含リン官能基;塩素原子又は臭素原子等のハロゲン原子を含む基等が挙げられ、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、めっき触媒又はその前駆体等への吸着能が高いことから、カルボン酸基、スルホン酸基、リン酸基、及びボロン酸基等のイオン性極性基、エーテル基、又はシアノ基が好ましく、カルボン酸基(カルボキシル基)又はシアノ基がより好ましい。
化合物Xには、相互作用性基が2種以上含まれていてもよい。
化合物X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X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。
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。
このような重合性基及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。
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)、及び、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。
なお、R1としては、水素原子、メチル基、又は、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、又は、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、又は、臭素原子で置換されたメチル基が好ましい。
L1としては、ポリマーの合成が容易で、金属層の密着性がより優れる点で、脂肪族炭化水素基、又は、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であるものがより好ましい。なお、ここで、L1の総炭素数とは、L1で表される置換又は無置換の2価の有機基に含まれる総炭素数を意味する。
また、上記相互作用性基ユニットの含有量は、めっき触媒又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。
ポリマーの第2の好ましい態様としては、下記式(A)、式(B)、及び式(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。
式(B)で表される繰り返し単位中のR5、X及びL2は、上記式(b)で表される繰り返し単位中のR5、X及び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又はその前駆体基を除く、めっき触媒又はその前駆体と相互作用する基を表す。なかでも、シアノ基又はエーテル基が好ましい。
式(C)中、Uは、単結合、又は、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及び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、金属層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-)、又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、又は、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及び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、金属層の密着性がより優れる点で、単結合、又は、2価の脂肪族炭化水素基、2価の芳香族炭化水素基、又はこれらを組み合わせた基であることが好ましい。
親水性基としては、めっき触媒又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、又は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。
式(A)で表される繰り返し単位の含有量は、反応性(硬化性又は重合性)及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、めっき触媒又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%が更に好ましい。
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。
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。
置換又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、又は、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。
置換又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、又は、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-、又は、-CO-脂肪族炭化水素基-が挙げられる。
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。
Qの価数nは、基板と金属層との密着性をより向上させる観点から、2以上であり、2以上6以下であることが好ましく、2以上5以下であることがより好ましく、2以上4以下であることが更に好ましい。
Qで表されるn価の連結基としては、例えば、式(1A)で表される基、式(1B)で表される基、
組成物Yは、相互作用性基を有する化合物、及び、重合性基を有する化合物を含む組成物である。つまり、被めっき層前駆体層が、相互作用性基を有する化合物、及び、重合性基を有する化合物の2種を含む。相互作用性基及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に含まれ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ことが好ましい。
重合性基を有する化合物とは、いわゆるモノマーであり、形成されるパターン状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、200~700がより好ましい。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以下であることがより好ましい。多官能モノマーとしては、具体的には、上述した式(1)で表される化合物が挙げられる。
重合性基を有する化合物には、相互作用性基が含まれていてもよい。
なお、相互作用性基を有する化合物と重合性基を有する化合物との質量比(相互作用性基を有する化合物の質量/重合性基を有する化合物の質量)は特に制限されないが、形成されるパターン状被めっき層の強度及びめっき適性のバランスの点で、0.1~10が好ましく、0.5~5がより好ましい。
例えば、被めっき層前駆体層には、モノマー(但し、上記式(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等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が挙げられるほか、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。
上記基板上のアンダーコート層の表面に被めっき層前駆体層を形成する方法は特に制限されず、基板上のアンダーコート層の表面に上述した各種成分を含む組成物を塗布して被めっき層前駆体層を形成する方法(塗布法)、又は、仮基板上に被めっき層前駆体層を形成して、基板上のアンダーコート層の表面に転写する方法(転写法)等が挙げられる。なかでも、厚みの制御がしやすい観点からは、塗布法が好ましい。
以下、塗布法の態様について詳述する。
なお、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、上述したアンダーコート層の形成に際して用いられる溶剤を使用することができる。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るほか、層厚の制御等がしやすい。
なお、基板の両面に被めっき層前駆体層を配置する場合には、基板の片面ずつに組成物を塗布してもよいし、組成物中に基板を浸漬して基板の両面に一度に塗布してもよい。
取り扱い性及び製造効率の観点からは、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、被めっき層前駆体層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。
次に、本発明の導電性フィルムの構成について詳述し、これに併せて本発明の導電性フィルムの製造方法、並びに、本発明のパターン状被めっき層付きフィルム及びその製造方法についても詳述する。
本発明の導電性フィルムは、基板と、上記基板上に配置されたアンダーコート層と、上記アンダーコート層上に配置されたパターン状被めっき層と、めっき処理によりパターン状被めっき層表面に積層された金属層とを有する。
図2は、本発明の導電性フィルムの実施形態の一例を示す断面模式図である。図2の導電性フィルム100は、基板12と、基板12上に配置されたアンダーコート層15と、アンダーコート層15上に配置されたパターン状被めっき層20と、めっき処理によりパターン状被めっき層20の表面に配置された金属層22とを有する。
以下、本発明の導電性フィルムについて、導電性フィルム100の製造方法を一例として図面を参照しながら説明する。また、併せて、本発明の被めっき層前駆体層付きフィルムの製造方法、及び、本発明のパターン状被めっき層付きフィルムの製造方法についても説明する。なお、本発明の実施形態は、以下に示した態様に限られるものではない。
工程1:基板上に、基板側からアンダーコート層を形成し、このアンダーコート層上に被めっき層前駆体層を形成する、被めっき層前駆体層付きフィルム形成工程、
工程2:被めっき層前駆体層にパターン露光を施しパターン状に硬化することでパターン状被めっき層を形成する、パターン状被めっき層付きフィルム形成工程、
工程3:めっき処理によりパターン状被めっき層上に金属層を形成する、金属層形成工程(導電フィルム形成工程)
工程1は、基板上に、アンダーコート層と被めっき層前駆体層とを基板側からこの順に積層形成して被めっき層前駆体層付きフィルムを形成する工程である。つまり、図1に示すような被めっき層前駆体層付きフィルム10を形成する工程である。
工程1では、まず、基板12上にアンダーコート層15を形成し、このアンダーコート層15の上に被めっき層前駆体層(未露光の塗膜)30を配置する。アンダーコート層15は、例えば、基板12上に上述した塗布法等により塗膜を形成した後、必要に応じて露光等で硬化することにより形成される。
工程2は、被めっき層前駆体層の塗膜に対してパターン状に露光を行い、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、図3Aに示すように、被めっき層前駆体層付きフィルム10を構成する被めっき層前駆体層30に対してフォトマスク25を介して黒矢印で示すようにパターン状に露光することにより重合性基の反応を促進させて硬化し、その後、未露光領域を除去してパターン状被めっき層20を得る工程(図3B)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付きフィルム50のパターン状被めっき層20は、相互作用性基の機能に応じて、後述する工程3でめっき触媒又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20は、めっき触媒又はその前駆体の良好な受容層として機能する。また、重合性基は、露光による硬化処理によって化合物同士の結合に利用され、硬さに優れたパターン状被めっき層を得ることができる。
基板上の塗膜にパターン状に露光する具体的な態様としては、赤外線レーザによる走査露光、マスクを用いたキセノン放電灯等の高照度フラッシュ露光、又は、マスクを用いた赤外線ランプ露光等が好適に挙げられる。塗膜を露光することにより、塗膜中の化合物に含まれる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。露光エネルギーとしては、10~8000mJ/cm2程度であればよく、好ましくは50~3000mJ/cm2の範囲である。
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、未露光領域を除去する場合は、露光された塗膜を有する基板を溶液中に浸漬させる方法(浸漬方法)、又は、露光された塗膜を有する基板上に現像液を塗布する方法(塗布方法)等が挙げられるが、浸漬方法が好ましい。浸漬方法の場合、浸漬時間としては生産性及び作業性等の観点から、1~30分程度が好ましい。
また、他の方法としては、使用される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。
パターン状被めっき層とは、上述した相互作用性基を含む層である。後述するように、パターン状被めっき層にはめっき処理が施される。
上記処理により形成されるパターン状被めっき層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、0.3~1.0μmが更に好ましい。
パターン状被めっき層のパターン形状は特に制限されず、後述する金属層を形成したい場所にあわせて調整され、例えば、メッシュパターン等が挙げられる。メッシュパターンの場合、メッシュパターン内の格子(開口部)の一辺の長さWは、800μm以下が好ましく、600μm以下がより好ましく、50μm以上が好ましく、400μm以上がより好ましい。なお、格子の形状は特に制限されず、略ひし形の形状、又は、多角形状(例えば、三角形、四角形、又は、六角形)としてもよい。また、一辺の形状を直線状の他、湾曲形状でもよいし、円弧状にしてもよい。
また、パターン状被めっき層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金属層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以下が更に好ましく、9μm以下が特に好ましく、7μm以下が最も好ましい。一方、その下限は、0.5μm以上が好ましく、1.0μm以上がより好ましい。
工程3は、上記工程2で形成されたパターン状被めっき層にめっき触媒又はその前駆体を付与して、めっき触媒又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金属層を形成する工程である。図3C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20上に金属層22が配置され、導電性フィルム100が得られる。
以下では、パターン状被めっき層にめっき触媒又はその前駆体を付与する工程(工程3-1)と、めっき触媒又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3-2)とに分けて説明する。
本工程では、まず、パターン状被めっき層にめっき触媒又はその前駆体を付与する。上述した、パターン状被めっき層中に含まれる相互作用性基が、その機能に応じて、付与されためっき触媒又はその前駆体を付着(吸着)する。より具体的には、パターン状被めっき層中及びパターン状被めっき層表面上に、めっき触媒又はその前駆体が付与される。
めっき触媒又はその前駆体は、めっき処理の触媒又は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又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又はその前駆体は、無電解めっき触媒又はその前駆体であることが好ましい。
この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めっき触媒前駆体とは、化学反応により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。めっき触媒前駆体である金属イオンは、還元反応によりめっき触媒である0価金属になる。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、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めっき触媒としてもよい。また、めっき触媒前駆体のままめっき浴に浸漬し、めっき浴中の還元剤により金属(めっき触媒)に変化させてもよい。
金属イオンは、金属塩を用いてパターン状被めっき層に付与することが好ましい。使用される金属塩としては、適切な溶剤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)、及び、M3/n(PO4)(Mは、n価の金属原子を表す)等が挙げられる。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。具体例としては、例えば、Agイオン、Cuイオン、Alイオン、Niイオン、Coイオン、Feイオン、及び、Pdイオンが挙げられ、なかでも、多座配位可能なものが好ましく、配位可能な官能基の種類数及び触媒能の点で、Agイオン又はPdイオンがより好ましい。
上記溶剤としては、水又は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、及び、ジメチルセロソルブ等を用いることができる。
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。
次に、めっき触媒又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、又は、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更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、銀鏡反応等によって、付着させた金属イオンを還元させて、所望のパターン状の金属層を形成してもよく、更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、及び、電解めっき処理の手順について詳述する。
本工程における無電解めっき処理は、例えば、金属イオンが付与されたパターン状被めっき層を備える基板を、水洗して余分な金属イオンを除去した後、無電解めっき浴に浸漬して行う。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。なお、無電解めっき浴中において、金属イオンの還元とこれに引き続き無電解めっきが行われる。
パターン状被めっき層中の金属イオンの還元は、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、無電解めっき処理前の別工程として行うことも可能である。触媒活性化液は、金属イオンを0価金属に還元できる還元剤を溶解した液で、液全体に対する還元剤の濃度が0.1~50質量%が好ましく、1~30質量%がより好ましい。還元剤としては、水素化ホウ素ナトリウム又はジメチルアミンボランのようなホウ素系還元剤、ホルムアルデヒド、及び、次亜リン酸等を使用することが可能である。
浸漬の際には、攪拌又は揺動を加えながら浸漬することが好ましい。
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必要があり、その点から、アセトン等のケトン類、又は、メタノール、エタノール及びイソプロパノール等のアルコール類が好ましい。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、及び、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、又は、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。
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、形成されるパターン状の金属層の厚みを適宜調整可能である。
電解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。なお、電解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、及び、亜鉛等が挙げられ、導電性の観点から、銅、金、又は、銀が好ましく、銅がより好ましい。
また、電解めっきにより得られる金属層の膜厚は、めっき浴中に含まれる金属濃度、又は、電流密度等を調整することで制御することができる。
また、金属層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、及び、亜鉛等が挙げられ、導電性の観点から、銅、金、又は、銀が好ましく、銅又は銀がより好ましい。
金属層のパターン形状は特に制限されないが、金属層はパターン状被めっき層上に配置されるため、パターン状被めっき層のパターン形状によって調整され、例えば、メッシュパターン等が挙げられる。メッシュパターンの金属層は、タッチパネル中のセンサー電極として好適に適用することができる。金属層はパターン形状がメッシュパターンの場合、メッシュパターン内の格子(開口部)の一辺の長さWの範囲、格子の形状の好適態様、及び、金属層の線幅は、上述したパターン状被めっき層の態様と同じである。
上記処理により得られた金属層を有する導電性フィルムは、種々の用途に適用でき、タッチパネル(又は、タッチパネルセンサー)、半導体チップ、各種電気配線板、FPC(Flexible printed circuits)、COF(Chip on Film)、TAB(Tape Automated Bonding)、アンテナ、多層配線基板、及び、マザーボード等の種々の用途に適用することができる。なかでも、タッチパネルセンサー(静電容量式タッチパネルセンサー)に用いることが好ましい。上記導電性積層体をタッチパネルセンサーに適用する場合、導電性フィルム中の金属層がタッチパネルセンサー中の検出電極又は引き出し配線として機能する。
なお、本明細書においては、タッチパネルセンサーと、各種表示装置(例えば、液晶表示装置、有機EL(エレクトロルミネッセンス)表示装置)を組み合わせたものを、タッチパネルと呼ぶ。タッチパネルとしては、いわゆる静電容量式タッチパネルが好ましく挙げられる。
(被めっき層形成用組成物の調液)
以下の成分を混合して、被めっき層形成用組成物を得た。
・イソプロパノール 94.9質量部
・ポリアクリル酸(和光純薬社製) 3質量部
・メチレンビスアクリルアミド(和光純薬社製) 2質量部
・IRGACURE127(BASF社製) 0.1質量部
まず、ロール状の厚み50μmのPET(ポリエチレンテレフタラート)フィルム(商品名「A4300」、東洋紡社製)の片面に、MT1007(日本ペイント社製)を乾燥後の膜厚が2μmになるように塗布した後、更にこれを80℃にて1分間乾燥することにより塗膜を形成した。次いで、メタルハライドのUV(ultraviolet)ランプを用いて上記塗膜を0.5J/cm2の露光量で光照射して硬化させることにより、アンダーコート層1を形成した。なお、後述する硬度評価及び摩擦係数評価は、このアンダーコート層1を基板上に有するフィルムを対象として実施した。そして、上記アンダーコート層1にラミネートフィルム(商品名「PAC2-50-THK」、サンエー化研社製)を貼り合わせた後、ロールに巻き取った。
なお、上記ロールtoロールにより被めっき層前駆体層付きフィルムR-1を製造する際には、PETフィルムの搬送途中で、PETフィルム上のアンダーコート層1及び2と接触するローラーも存在する。
作製した被めっき層前駆体層付きフィルムR―1を150mm角に切断した。次いで、切断した被めっき層前駆体層付きフィルムR―1の被めっき層前駆体層2に対して、導電パターンを付与した150mm角のマスク越しに高圧水銀ランプを用いて1J/cm2照射した。その後、40℃の水をシャワー状に2分間噴霧してパターン状に現像することにより、パターン状被めっき層付きフィルムR2-1を得た。
次に、得られたパターン状被めっき層付きフィルムR2-1を、上村工業社製のPd触媒付与液「MAT」の「MAT-A液」のみを4倍に薄めたPdイオン付与液に5分間浸漬させ、浸漬後、パターン状被めっき層付きフィルムR2-1を洗浄した。その後、得られたパターン状被めっき層付きフィルムR2-1を上村工業のPd還元剤「MAB」に5分間浸漬した。次いで、浸漬後のパターン状被めっき層付きフィルムR2-1を、上村工業社製のめっき液「PEA」に5分間浸漬することにより被めっき層上にパターン状に銅を析出させて、導電性フィルムR3-1を得た。
まず、ロール状の厚み50μmのPET(ポリエチレンテレフタラート)フィルム(商品名「A4300」、東洋紡社製)の片面に、HNBR(水素添加ニトリルゴム、Zetpole0020:日本ゼオン製)をシクロヘキサノンに10質量%溶解させた組成物を乾燥後の膜厚が2μmになるように塗布した後、更にこれを80℃にて1分間乾燥することにより塗膜を形成した。次いで、メタルハライドのUV(ultraviolet)ランプを用いて上記塗膜を0.5J/cm2の露光量で光照射して硬化させることにより、アンダーコート層1を形成した。
得られた基板上にアンダーコート層1が形成されたフィルムを、アンダーコート層1がローラー面側となるようにしてロール搬送したところ、ローラーに接触すると滑らないためにヨレが生じ、ロールが回転しなかった。つまり、ロールハンドリングすることができなかった。
(実施例1)
表1に示す組成比に基づいて、ジオール化合物(表中、「ジオール成分」)としてポリエチレングリコール(PEG Mw(重量平均分子量):400 東京化成工業社製)及びエトキシ化イソプロピリデンジフェノール(ビスフェノールA-EO付加 Aldrich社製)と、ジイソシアネート化合物(表中、「ジイソシアネート成分」)としてイソホロンジイソシアネート(IPDI 和光純薬社製)をメチルエチルケトンに溶解させて60℃で5時間攪拌した。
得られた重合物に開始剤としてIrgacure2959(固形成分に対する質量比1% BASF社製)を加え、添加剤としてポリジメチルシロキサン(重量平均分子量770、固形成分に対する質量比0.1%、Alfa Aesar社製)を加えてアンダーコート材料1とした。
表1に、上記アンダーコート材料1の組成をまとめて示す。なお、溶剤は、アンダーコート材料1の組成物全質量が100質量部となるように添加し、更にメチルエチルケトンとPGMEA(propyleneglycol monomethyl ether acetate)の配合比(質量比)が7:3となるように調製した。
表1に記載の成分とした以外は上記アンダーコート材料1と同様の方法により、アンダーコート材料2を調製した。また、上記アンダーコート材料2を用いてアンダーコート層1及びアンダーコート層2(それぞれ乾燥後の膜厚が2μm)を作製した以外は、比較例1と同様の方法により被めっき層前駆体層付きフィルムT―2を作製した。また、比較例1と同様の方法によりパターン状被めっき層付きフィルムT2-2、導電性フィルムT3-2を得た。
表1に記載の成分とした以外は上記アンダーコート材料1と同様の方法により、アンダーコート材料3を調製した。また、上記アンダーコート材料3を用いてアンダーコート層1及びアンダーコート層2(それぞれ乾燥後の膜厚が2μm)を作製した以外は、比較例1と同様の方法により被めっき層前駆体層付きフィルムT―3を作製した。また、比較例1と同様の方法によりパターン状被めっき層付きフィルムT2-3、導電性フィルムT3-3を得た。
表1に記載の成分とした以外は上記アンダーコート材料1と同様の方法により、アンダーコート材料4を調製した。また、上記アンダーコート材料4を用いてアンダーコート層1及びアンダーコート層2(それぞれ乾燥後の膜厚が2μm)を作製した以外は、比較例1と同様の方法により被めっき層前駆体層付きフィルムT―4を作製した。また、比較例1と同様の方法によりパターン状被めっき層付きフィルムT2-4、導電性フィルムT3-4を得た。
表1に記載の成分とした以外は上記アンダーコート材料1と同様の方法により、アンダーコート材料5を調製した。また、上記アンダーコート材料5を用いてアンダーコート層1及びアンダーコート層2(それぞれ乾燥後の膜厚が2μm)を作製した以外は、比較例1と同様の方法により被めっき層前駆体層付きフィルムT―5を作製した。また、比較例1と同様の方法によりパターン状被めっき層付きフィルムT2-5、導電性フィルムT3-5を得た。
表1に記載の成分とした以外は上記アンダーコート材料1と同様の方法により、アンダーコート材料6を調製した。また、上記アンダーコート材料6を用いてアンダーコート層1及びアンダーコート層2(それぞれ乾燥後の膜厚が2μm)を作製した以外は、比較例1と同様の方法により被めっき層前駆体層付きフィルムT―6を作製した。また、比較例1と同様の方法によりパターン状被めっき層付きフィルムT2-6、導電性フィルムT3-6を得た。
表1に記載の成分とした以外は上記アンダーコート材料1と同様の方法により、アンダーコート材料7を調製した。また、上記アンダーコート材料7を用いてアンダーコート層1及びアンダーコート層2(それぞれ乾燥後の膜厚が2μm)を作製した以外は、比較例1と同様の方法により被めっき層前駆体層付きフィルムT―7を作製した。また、比較例1と同様の方法によりパターン状被めっき層付きフィルムT2-7、導電性フィルムT3-7を得た。
表1に記載の成分とした以外は上記アンダーコート材料1と同様の方法により、アンダーコート材料8を調製した。また、上記アンダーコート材料8を用いてアンダーコート層1及びアンダーコート層2(それぞれ乾燥後の膜厚が2μm)を作製した以外は、比較例1と同様の方法により被めっき層前駆体層付きフィルムR-3を作製した。また、比較例1と同様の方法によりパターン状被めっき層付きフィルムR2-3、導電性フィルムR3-3を得た。
表1に記載の成分とした以外は上記アンダーコート材料1と同様の方法により、アンダーコート材料9を調製した。また、上記アンダーコート材料9を用いてアンダーコート層1及びアンダーコート層2(それぞれ乾燥後の膜厚が2μm)を作製した以外は、比較例1と同様の方法により被めっき層前駆体層付きフィルムR-4を作製した。また、比較例1と同様の方法によりパターン状被めっき層付きフィルムR2-4、導電性フィルムR3-4を得た。
表1に記載の成分とした以外は上記アンダーコート材料1と同様の方法により、アンダーコート材料10を調製した。また、上記アンダーコート材料10を用いてアンダーコート層1及びアンダーコート層2(それぞれ乾燥後の膜厚が2μm)を作製した以外は、比較例1と同様の方法により被めっき層前駆体層付きフィルムR-5を作製した。また、比較例1と同様の方法によりパターン状被めっき層付きフィルムR2-5、導電性フィルムR3-5を得た。
表1に記載の成分とした以外は上記アンダーコート材料1と同様の方法により、アンダーコート材料11を調製した。また、上記アンダーコート材料11を用いてアンダーコート層1及びアンダーコート層2(それぞれ乾燥後の膜厚が2μm)を作製した以外は、比較例1と同様の方法により被めっき層前駆体層付きフィルムR-6を作製した。また、比較例1と同様の方法によりパターン状被めっき層付きフィルムR2-6、導電性フィルムR3-6を得た。
表1中、各成分の配合量は「質量部」を基準とする。また、溶剤は、アンダーコート材料1の組成物全質量が100質量部となるように添加し、更にメチルエチルケトンとPGMEAの配合比(質量比)が7:3となるように調製した。
また、アンダーコート材料1~7の各ウレタン(メタ)アクリレートは、重量平均分子量は30,000~70,000の範囲内であった。
・ジオール成分
ポリエチレングリコール(PEG Mw:400 東京化成工業社製)
ポリエチレングリコール(PEG Mw:1000 東京化成工業社製)
ポリテトラメチレンオキシド(PTMO Mw:650和光純薬社製)
エトキシ化イソプロピリデンジフェノール(ビスフェノールA-EO付加 Aldrich社製)
・ジイソシアネート成分
イソホロンジイソシアネート(IPDI 和光純薬社製)
ヘキサメチレンジイソシアネート(HDI 東京化成工業社製)
・架橋成分
ヒドロキシエチルアクリレート(HEA 東京化成工業社製)
ヒドロキシブチルアクリレート(HBA 東京化成工業社製)
ジペンタエリスリトールヘキサアクリレート(DPHA Aldrich社製)
・触媒
ジラウリン酸ジブチル錫(和光純薬社製)
・重合開始剤
Irgacure2959(BASF社製)
・添加剤
ポリジメチルシロキサン(重量平均分子量770、Alfa Aesar社製)
上記アンダーコート層1及びアンダーコート層2を設けず、PETフィルム(商品名「A4300」、東洋紡社製)の両面に、被めっき層形成用組成物からなる被めっき層前駆体層1及び被めっき層前駆体層2を直接形成した以外は、比較例1と同様の方法により被めっき層前駆体層付きフィルムR-7を作製した。また、比較例1と同様の方法によりパターン状被めっき層付きフィルムR2-7、導電性フィルムR3-7を得た。
上記で得られた実施例及び比較例の各被めっき層前駆体層付きフィルム、パターン状被めっき層付きフィルム、又は導電性フィルムを用いて、下記に示す評価を行った。
アンダーコート層1が形成された基板に対して硬度評価を実施した。
具体的には、フィッシャーインスツルメンツ社製HM500型皮膜硬度計を用いて先端曲率半径0.2mmの球状圧子を上記アンダーコート層1の表面に接触させ、最大荷重2mN、負荷時間10secの条件でユニバーサル硬度(N/mm2)を測定した。結果を表2に示す。
アンダーコート層1が形成された基板に対して摩擦係数評価を実施した。
具体的には、まず、離形紙であるセラピール38BKE(東レ社製)を、その離形面が上記アンダーコート層1の表面に接するようにして、力をかけずに乗せた。次いで、その上に100gの分銅を乗せて水平方向に100mm/minの速度でセラピールを動かしたときにかかる荷重を、フォースゲージFGX-2(日本電産シンポ社製)を用いて測定した。摩擦係数は、上記の測定値(荷重)を分銅重さで除すことにより求めた。結果を表2に示す。
上述した比較例1のロールtoロール方法により被めっき層前駆体層付きフィルムを製造できる場合を「A」、製造できない場合を「B」とした。結果を表2に示す。
作製したパターン状被めっき層付きフィルムを30℃、pH13.5の水酸化ナトリウム水溶液に15分浸漬させ、パターン状被めっき層の状態を光学顕微鏡で観察することにより、アルカリ耐性の評価を実施した。アルカリ耐性の評価は、以下の基準により行った。結果を表2に示す。
「A」:パターン状被めっき層の状態が変化しなかった。
「B」:パターン状被めっき層の剥がれは観察されないが、色味が変化した。
「C」:パターン状被めっき層の剥がれが観察された。
作製した導電性フィルムのパターン状の金属層にニチバン製密着試験用テープCT―24を貼りつけて十分に密着させた後、上記試験用テープを一気に剥離させることにより、密着性試験を実施した。密着性の評価は、以下の基準により行った。結果を表2に示す。
「A」:金属層の剥離が観察されなかった。
「B」:パターンの面積中、10%未満の範囲で剥離が観察された。
「C」:パターンの面積中、10%以上の範囲で剥離が観察された。
上記で作製したT3-1~T3-7の導電性フィルムの金属層のパターン形状をタッチパネル用の配線パターンとした導電性フィルムを作製し、タッチパネルとして反応するかどうか確認したところ、いずれも問題なく反応した。
50 パターン状被めっき層付きフィルム
12 基板
15 アンダーコート層
20 パターン状被めっき層
22 金属層
25 フォトマスク
30 被めっき層前駆体層
100 導電性フィルム
Claims (6)
- 基板と、前記基板上に配置されたアンダーコート層と、前記アンダーコート層上に配置された被めっき層前駆体層と、を有する被めっき層前駆体層付きフィルムであって、
前記アンダーコート層は、その表面における硬度が10N/mm2以下であり、且つ、離形紙との摩擦係数が5以下である、被めっき層前駆体層付きフィルム。 - 前記被めっき層前駆体層が、重合開始剤と、以下の化合物X又は組成物Yとを含む、請求項1に記載の被めっき層前駆体層付きフィルム。
化合物X:めっき触媒又はその前駆体と相互作用する官能基、及び、重合性基を有する化合物
組成物Y:めっき触媒又はその前駆体と相互作用する官能基を有する化合物、及び、重合性基を有する化合物を含む組成物 - 基板と、前記基板上に配置されたアンダーコート層と、前記アンダーコート層上に配置されたパターン状被めっき層と、を有するパターン状被めっき層付きフィルムであって、
前記アンダーコート層は、その表面における硬度が10N/mm2以下であり、且つ、離形紙との摩擦係数が5以下である、パターン状被めっき層付きフィルム。 - 請求項3に記載のパターン状被めっき層付きフィルムと、前記パターン状被めっき層付きフィルム中の前記パターン状被めっき層上に配置された金属層とを有する、導電性フィルム。
- 前記金属層が、無電解めっき処理により形成された、請求項4に記載の導電性フィルム。
- 請求項4又は請求項5に記載の導電性フィルムを含む、タッチパネル。
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KR1020187025927A KR20180112818A (ko) | 2016-03-11 | 2017-03-03 | 피도금층 전구체층 부착 필름, 패턴 형상 피도금층 부착 필름, 도전성 필름, 터치 패널 |
JP2018504451A JP6803906B2 (ja) | 2016-03-11 | 2017-03-03 | 被めっき層前駆体層付きフィルム、パターン状被めっき層付きフィルム、導電性フィルム、タッチパネル |
CN201780015829.0A CN108778710B (zh) | 2016-03-11 | 2017-03-03 | 带被镀层前体层的薄膜、带图案状被镀层的薄膜、导电性薄膜及触摸面板 |
US16/115,886 US20180371618A1 (en) | 2016-03-11 | 2018-08-29 | Film having plated-layer precursor layer, film having patterned plated layer, electroconductive film, and touch panel |
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US16/115,886 Continuation US20180371618A1 (en) | 2016-03-11 | 2018-08-29 | Film having plated-layer precursor layer, film having patterned plated layer, electroconductive film, and touch panel |
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CN108762576B (zh) * | 2018-06-11 | 2022-04-15 | 业成科技(成都)有限公司 | 触控模组及其制作方法 |
BR112022014065A2 (pt) * | 2020-01-20 | 2022-09-13 | Basf Se | Usos de uma folha e de um dispositivo, e, dispositivo para liberação controlada de uma composição odorífera |
CN113809509B (zh) * | 2020-06-11 | 2023-07-18 | 华为技术有限公司 | 一种天线成型方法、盖板组件及终端设备 |
CN113485581A (zh) * | 2021-07-02 | 2021-10-08 | 浙江鑫柔科技有限公司 | 一种用于在基板上形成金属网格的方法 |
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- 2017-03-03 WO PCT/JP2017/008551 patent/WO2017154786A1/ja active Application Filing
- 2017-03-03 CN CN201780015829.0A patent/CN108778710B/zh active Active
- 2017-03-03 KR KR1020187025927A patent/KR20180112818A/ko not_active Application Discontinuation
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JPS543843A (en) * | 1977-06-11 | 1979-01-12 | Showa Highpolymer Co Ltd | Surface treatment of base material for imparting electrical conductivity |
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JP2014108531A (ja) * | 2012-11-30 | 2014-06-12 | Mitsubishi Paper Mills Ltd | 銀めっき塗装体 |
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CN108778710B (zh) | 2021-03-23 |
JPWO2017154786A1 (ja) | 2018-12-13 |
KR20180112818A (ko) | 2018-10-12 |
CN108778710A (zh) | 2018-11-09 |
US20180371618A1 (en) | 2018-12-27 |
JP6803906B2 (ja) | 2020-12-23 |
TWI759284B (zh) | 2022-04-01 |
TW201732517A (zh) | 2017-09-16 |
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