WO2014010270A1 - 導電積層体、パターン化導電積層体、その製造方法、および、それらを用いてなるタッチパネル - Google Patents
導電積層体、パターン化導電積層体、その製造方法、および、それらを用いてなるタッチパネル Download PDFInfo
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- WO2014010270A1 WO2014010270A1 PCT/JP2013/058043 JP2013058043W WO2014010270A1 WO 2014010270 A1 WO2014010270 A1 WO 2014010270A1 JP 2013058043 W JP2013058043 W JP 2013058043W WO 2014010270 A1 WO2014010270 A1 WO 2014010270A1
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- conductive
- layer
- conductive laminate
- inorganic particles
- patterned
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/02—Layer formed of wires, e.g. mesh
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- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06F—ELECTRIC DIGITAL DATA PROCESSING
- G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
- G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
- G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
- G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
- B32B2307/202—Conductive
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
- B32B2457/202—LCD, i.e. liquid crystal displays
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
- B32B2457/206—Organic displays, e.g. OLED
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
- B32B2457/208—Touch screens
Definitions
- the present invention relates to a conductive laminate and a patterned conductive laminate comprising a conductive region and a non-conductive region. More specifically, the present invention relates to a patterned conductive laminate having high non-visibility of a pattern portion composed of a conductive region and a non-conductive region. Furthermore, the present invention relates to a patterned conductive laminate used for electrode members used in displays related to liquid crystal displays, organic electroluminescence, electronic paper and the like and solar cell modules.
- conductive regions and non-conductive regions are processed by forming a non-conductive region in the conductive layer of the conductive member. A desired pattern composed of regions is formed and used.
- a conductive member with a conductive layer laminated on a substrate uses a conventional conductive thin film such as ITO or a metal thin film, as well as a linear conductive material such as a metal nanowire.
- a conductive laminate in which a resin layer is laminated on a conductive layer using metal nanowires as a conductive component has been proposed (Patent Document 1).
- distributed metal nanowire in the matrix of the high curing degree using a polyfunctional component is proposed (patent document 2).
- a conductive laminate using metal nanowires that has been patterned into a conductive region and a nonconductive region that leaves the metal nanowires has also been proposed (Patent Document 3).
- Patent Document 4 a chemical etching method using a photoresist or an etching solution is generally used.
- the conductive laminate described in Patent Document 1 has a difference in the abundance of conductive components between the conductive region and the non-conductive region when a pattern composed of the conductive region and the non-conductive region is formed. There is a problem in that the pattern is recognized (that is, non-visibility is low).
- the conductive laminate described in Patent Document 2 has a small difference in refractive index between the base material and the conductive layer, and the conductive laminate described in Patent Document 3 is used.
- the body has a small difference in the residual amount of the conductive component between the conductive region and the non-conductive region, there is still a problem that the non-visibility of the pattern is low.
- a chemical etching method as described in Patent Document 4 is generally used as a pattern forming method of the conductive laminate, and improvement of pattern non-visibility by using the patterning method is desired. Yes.
- the present invention is intended to obtain a patterned conductive laminate having high non-visibility of a pattern portion.
- the present invention employs the following configuration. That is, (1) A conductive laminate having a conductive layer on at least one surface of a substrate, the conductive layer including a metal-based linear structure having a network structure, and inorganic particles in any layer of the conductive laminate. A conductive laminate comprising the conductive laminate. (2) The conductive laminate according to (1), comprising a layer containing inorganic particles between the substrate and the conductive layer.
- the conductive laminate according to (1), wherein the inorganic particles have an average particle size of 500 nm or less.
- the conductive laminate as described in (1) above, wherein the inorganic particles are carbonates.
- Electronic paper using the display according to (13).
- the present invention it is possible to provide a conductive laminate in which the non-visibility of the pattern portion becomes high after the pattern is formed, and a patterned conductive laminate in which the non-visibility of the pattern portion is high.
- the cross-sectional schematic diagram of the electrically conductive laminated body which contained the inorganic particle in the undercoat layer of this invention The cross-sectional schematic diagram of the electrically conductive laminated body which contained the inorganic particle in the electrically conductive layer of this invention.
- the cross-sectional schematic diagram of the electrically conductive laminated body which contained the inorganic particle in the back surface hard-coat layer of this invention The cross-sectional schematic diagram of the electrically conductive laminated body which contained the inorganic particle in the easily bonding layer of this invention.
- the cross-sectional schematic diagram of the patterned electroconductive laminated body which contained the void in the undercoat layer of this invention The cross-sectional schematic diagram of the electrically conductive laminated body which contained the void in the undercoat layer of this invention.
- the cross-sectional schematic diagram of the patterned conductive laminated body containing the void in the patterned conductive layer of this invention The cross-sectional schematic diagram of the patterned electrically conductive laminated body which contained the void in the back surface hard-coat layer of this invention.
- the cross-sectional schematic diagram of the patterned electroconductive laminated body which contained the void in the easily bonding layer of this invention An example of a metal-based linear structure having a network structure. A touch panel on which the conductive laminate of the present invention is mounted.
- the conductive laminate of the present invention has a conductive layer on at least one side of the substrate. That is, you may have a conductive layer only on the single side
- the conductive layer is formed by containing a conductive component having a network structure made of a metal-based linear structure in a matrix made of a polymer having a crosslinked structure. If the conductive component having a network structure composed of a metal-based linear structure is randomly oriented, good optical properties can be obtained in addition to conductivity and durability, so the conductive laminate of the present invention is used.
- the displayed body is preferable because the display image becomes clear.
- Various functional layers such as a hard coat layer and an undercoat layer can be provided on the conductive laminate as necessary.
- the hard coat layer can be provided on the outermost layer on the side where the conductive layer of the conductive laminate is formed, or on the outermost layer on the opposite side across the substrate.
- the hard coat layer is provided mainly for improving the surface strength, antifouling property, fingerprint resistance and the like, and can further impart antiglare property by forming fine irregularities on the surface.
- a thermosetting acrylic resin or an ultraviolet curable acrylic resin is preferably used from the viewpoint of excellent properties such as transparency and hardness when cured.
- the undercoat layer is provided between the base material and the conductive layer, and is mainly provided for the purpose of improving the adhesion between the base material and the conductive layer.
- the undercoat layer a thermosetting or ultraviolet curable polyester resin or acrylic resin is preferably used from the viewpoint of adhesion to a substrate and a conductive layer and transparency. If the conductive laminate of the present invention contains inorganic particles to be described later in any of the above layers, the effect of improving the invisibility of the pattern after patterning can be exhibited. In addition, when inorganic particles are included in the conductive layer or the undercoat layer, when the chemical etching method is adopted, the effect of improving the invisibility of the pattern simultaneously with the patterning of the conductive layer is exhibited. It is desirable that the conductive layer and / or the undercoat layer contain inorganic particles from the viewpoint of manufacturing cost reduction due to the reduction.
- the material for the base material in the conductive laminate of the present invention include transparent resin and glass.
- the resin include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyamide, polyimide, polyphenylene sulfide, aramid, polyethylene, polypropylene, polystyrene, polylactic acid, polyvinyl chloride, polycarbonate, polymethyl methacrylate, etc.
- Acrylic / methacrylic resins alicyclic acrylic resins, cycloolefin resins, triacetyl cellulose, acrylonitrile butadiene styrene copolymer synthetic resins (ABS), polyvinyl acetate, melamine resins, phenolic resins, polyvinyl chloride and polyvinyl chloride Examples include resins containing chlorine atoms (Cl atoms) such as vinylidene, resins containing fluorine atoms (F atoms), silicone resins, and mixtures and / or copolymers of these resins.
- the glass can be used ordinary soda glass. Moreover, these several base materials can also be used in combination.
- a composite substrate such as a substrate in which a resin and glass are combined and a substrate in which two or more kinds of resins are laminated may be used.
- the shape of the base material it may be a film that can be wound up with a thickness of 250 ⁇ m or less, or a substrate with a thickness of more than 250 ⁇ m, as long as it is within the range of the total light transmittance described later.
- a resin film of 250 ⁇ m or less is preferable, more preferably 190 ⁇ m or less, still more preferably 150 ⁇ m or less, and particularly preferably 100 ⁇ m or less.
- a resin film As a base material, what was made into the film by unstretching, uniaxial stretching, and biaxial stretching of resin can be applied.
- these resin films from the viewpoint of moldability to a substrate, optical properties such as transparency, productivity, etc., polyester films such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), and mixing with PEN and A copolymerized PET film or polypropylene film can be preferably used.
- the resin film used for a base material may be an easily adhesive film in which an easily adhesive layer is provided on one side or both sides.
- Examples of the metal-based linear structure in the present invention include fibrous conductors, nanowires, acicular conductors such as whiskers and nanorods.
- the shape is not particularly limited, and may be linear or curved, or may have a shape having a linear portion and / or a curved portion in a part thereof.
- the nanowire is a structure having an arc shape as exemplified by reference numeral 14 in FIG. 7, and the needle shape is a linear shape as exemplified by reference numeral 15 in FIG.
- the metal-based linear structure may exist in the form of an aggregate in addition to the case where it exists alone.
- the orientation of the arrangement of the metal-based linear structures may not be regular and may be in a randomly aggregated state, and the long surfaces of the metal-based linear structures are parallel to each other. It may be in a gathered state.
- a state in which the surfaces in the major axis direction are gathered in parallel it is known that it becomes an aggregate called a bundle, and the metal-based linear structure may have a similar bundle structure.
- the metal-based linear structure preferably used in the present invention is a metal nanowire, and the metal composition of the metal nanowire is not particularly limited, and is composed of one or more metals of a noble metal element, a noble metal oxide, and a base metal element.
- a noble metal element e.g, gold, platinum, silver, palladium, rhodium, iridium, ruthenium, osmium, etc.
- at least one metal belonging to the group consisting of iron, cobalt, copper, tin Preferably, it contains silver at least from the viewpoint of conductivity.
- Nanowires of noble metals and noble metal oxides that can be used as metal-based linear structures are described in JP-T 2009-505358, JP-A 2009-129607, JP-A 2009-070660,
- the needle crystals such as whiskers or fibers of metal oxide include, for example, WK200B of DENTOR WK series (manufactured by Otsuka Chemical Co., Ltd.), which is a composite oxide of potassium titanate fiber, tin and antimony oxide. , WK300R and WK500 are commercially available.
- the network structure is a dispersion structure in which the average number of contacts with another metal-based linear structure exceeds at least 1 when viewed with respect to individual metal-based linear structures in the conductive layer. It means having.
- the contact may be formed between any part of the metal-based linear structure, the end parts of the metal-based linear structure are in contact with each other, or the terminal and the part other than the end of the metal-based linear structure Or portions other than the ends of the metal-based linear structure may be in contact with each other.
- the contact may mean that the contact is joined or simply in contact. Note that, among the metal-based linear structures in the conductive layer, some metal-based linear structures that do not contribute to the formation of the network (that is, the contacts are 0 and exist independently of the network). May be present.
- the conductive layer in the present invention preferably contains the metal-based linear structure in a matrix made of a polymer having a crosslinked structure.
- Matrix components include organic or inorganic polymers.
- examples of the inorganic polymer include inorganic oxides such as silicon oxide formed by hydrolysis / polymerization reaction from trialkoxysilanes and the like, and silicon oxide formed by sputter deposition. It is done.
- trialkoxysilanes used in this case include tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, and methyltrisilane.
- Methoxysilane methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, i-propyltrimethoxysilane, i-propyltriethoxysilane, n-butyltri Methoxysilane, n-butyltriethoxysilane, n-pentyltrimethoxysilane, n-pentyltriethoxysilane, n-hexyltrimethoxysilane, n-heptyltrimethoxysilane, n-octyltrimethoxysilane Vinyltrimethoxysilane, vinyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, phenyltri
- organic polymer examples include a thermosetting resin and a photocurable resin.
- a polyester resin a polycarbonate resin, an acrylic resin, a methacrylic resin, an epoxy resin, and a polyamide resin such as nylon or benzoguanamine.
- ABS resin polyimide resin, olefin resin such as polyethylene and polypropylene, polystyrene resin, polyvinyl acetate resin, melamine resin, phenol resin, containing chlorine atoms (Cl atoms) such as polyvinyl chloride and polyvinylidene chloride
- Organic polymers such as resins containing fluorine atoms (F atoms), silicone resins, and cellulose resins, and those having a crosslinked structure in the structure of these polymers, These polymers and a crosslinking agent may be reacted to form a crosslinked polymer. At least one kind selected from the characteristics and productivity required from these organic polymers may be used, and two or more kinds thereof may be mixed and used.
- the organic polymer is preferably composed of a polymer having a structure in which a compound having three or more carbon-carbon double bond groups is polymerized.
- Such an organic polymer is made from a composition containing at least one selected from the group consisting of monomers, oligomers and polymers having three or more functional groups containing carbon-carbon double bonds as a raw material. It can obtain by carrying out a polymerization reaction using as a reaction point.
- Examples of the functional group containing a carbon-carbon double bond include a vinyl group, an isopropenyl group, an isopentenyl group, an allyl group, an acryloyl group, a methacryloyl group, an acryloyloxy group, a methacryloyloxy group, a methacryl group, an acrylamide group, and a methacryl group.
- a halogen atom such as fluorine or chlorine
- a carbon-carbon double bond having a substituent having an aromatic ring such as a phenyl group or a naphthyl group (for example, a styryl group) or a butadienyl group (for example, CH 2 ⁇ C (R1 ) —C (R2) ⁇ CH—, CH 2 ⁇ C (R1) —C ( ⁇ CH 2 ) — (wherein R1, R2 are H or CH 3 )), and the like include a group having a conjugated polyene structure Can be mentioned. In consideration of the characteristics and productivity required from these, one type or a mixture of two or more types may be used.
- Examples of the compound having three or more carbon-carbon double bonds that contribute to the polymerization reaction include pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, pentaerythritol ethoxytriacrylate, and pentaerythritol.
- compositions obtained by polymerizing a single substance or a mixture of two or more polymerized alone, or a dimer or more oligomer in which two or more kinds are copolymerized can be used, it is not specifically limited to these.
- a compound having 4 or more carbon-carbon double bond groups contributing to the polymerization reaction that is, a compound having 4 or more functional groups can be more preferably used.
- tetrafunctional or higher functional compound examples include the tetrafunctional tetraacrylate, tetramethacrylate, pentafunctional pentaacrylate, pentamethacrylate, hexafunctional hexaacrylate, hexamethacrylate, and the like.
- the conductive laminate in the present invention preferably contains inorganic particles in any of the layers.
- the inorganic particles in the layer are dissolved by chemical treatment to generate voids, thereby exhibiting an effect of changing the optical characteristics.
- various carbonates, inorganic compounds that can be dissolved by acid treatment such as zinc oxide, tin oxide and ITO can be used.
- carbonates are preferably used from the viewpoints of easy reaction with acids, stability to water and alkaline solutions, organic solvents, and formation of voids when reacting with acids, and formation of voids.
- Inexpensive calcium carbonate is more preferably used.
- the size of the inorganic particles is preferably an average particle size of 500 nm or less because the layer containing the inorganic particles can be thinned, and more preferably an average particle size of 300 nm or less in order to suppress a decrease in the transmittance and haze value of the conductive laminate.
- the average particle diameter a of the inorganic particles is defined as a mode value obtained from a distribution curve based on the number of major axes.
- the long diameter is the longest diameter that can be recognized on an image taken with a microscope for each individual inorganic particle.
- SEM field emission scanning electron microscope
- the average particle diameter of the inorganic particles in the present invention refers to the primary particle diameter of the inorganic particles if monodispersed, and refers to the particle diameter of the aggregated particles if the aggregate is an aggregate of a plurality of primary particles.
- the aggregate is photographed with a microscope, the longest diameter recognizable on the image is regarded as the major axis of the particle, and the average particle diameter a is calculated by the method described above.
- the patterned conductive layer body in the present invention includes voids in any layer of the non-conductive region.
- the voids exhibit the effect of reducing the transmission haze value and the diffuse reflection light in the non-conductive region.
- the transmission haze value and the diffuse reflected light decrease due to the fact that there are fewer metal-based linear structures than the conductive region, but in the present invention, the difference in optical characteristics as described above is reduced.
- a patterned conductive layer body with improved pattern non-visibility can be obtained.
- the void size in the present invention is preferably an average void diameter of 500 nm or less because the void-containing layer can be thinned, effectively suppressing a decrease in transmittance and an increase in transmission haze value in the non-conductive region of the patterned conductive laminate.
- an average void diameter of 300 nm or less is more preferable.
- the measurement method of the average void diameter is the same as the average particle diameter of the inorganic particles described in the above [Inorganic particles].
- a void having a major axis of 10 nm or more that can be confirmed by an SEM observation image is defined as a void in the present invention.
- the void in the present invention is generated by dissolving or decomposing the aforementioned inorganic particles.
- inorganic particles are decomposed by infiltrating an acid or alkaline solution into the layer containing inorganic particles and dissolving the inorganic particles by chemical reaction to generate voids, or by applying energy from the outside, such as heating or laser.
- a method of generating voids from the point that it can be applied to a fine patterned conductive layer and other steps, it can be performed at the same time, and from the point of good productivity, the solution is infiltrated and the inorganic particles are dissolved by a chemical reaction to void.
- the method of generating is preferably used.
- the layer containing inorganic particles in the present invention can be disposed at any position in the conductive laminate.
- it can be arranged as an undercoat layer between the substrate and the conductive layer, or can be arranged as a hard coat layer on the opposite side of the conductive layer.
- the average particle diameter of the inorganic particles has a preferable range in order to obtain the effects of the present invention, and the layer containing the inorganic particles is sufficient to embed the inorganic particles. If there is a sufficient layer thickness, it is preferable. Specifically, a layer thickness of 200 nm or more is desirable.
- the layer thickness is less than 200 nm, irregularities due to inorganic particles that could not be embedded may occur and transparency may be lowered.
- the inorganic particles are dissolved, they flow out without generating voids in the layer, and thus there may be a case where a change in optical characteristics which is an effect of the present invention cannot be obtained.
- the layer containing inorganic particles is preferably an undercoat layer or an easily adhesive layer of a substrate that does not affect the patterning property and the contact resistance depending on the layer thickness.
- composition of the layer containing inorganic particles a polymer having a crosslinked structure similar to that described in the above [Matrix] section can be preferably used.
- the layer containing inorganic particles in the present invention can be disposed at any position of the conductive laminate, but is preferably disposed between the base material and the conductive layer.
- the conductive layer when the conductive layer is provided only on one side of the substrate, it is preferable to have a layer containing inorganic particles between the substrate and the conductive layer.
- the substrate when it has a conductive layer on both surfaces of the substrate, (i) it may have a layer containing inorganic particles between any of the conductive layers formed on both surfaces of the substrate and the substrate. ii) You may have the layer containing an inorganic particle between any one conductive layer and the base material of the conductive layer formed in both surfaces of the base material.
- a method for forming a layer containing inorganic particles a method in which inorganic particles are dispersed in a composition solution of a layer containing inorganic particles and coated on a substrate is suitably used.
- coating methods include casting, spin coating, dip coating, bar coating, spraying, blade coating, slit die coating, gravure coating, reverse coating, screen printing, mold coating, printing transfer, and wet coating methods such as inkjet.
- a wet coating method using slit die coating or micro gravure is preferable because it can be applied uniformly in a roll-to-roll manner with high productivity.
- the easily bonding layer solution which disperse
- the patterned conductive laminate of the present invention has a patterned conductive layer on at least one side of the substrate.
- the patterned conductive layer has a conductive region and a non-conductive region in its plane.
- the conductive region includes a metal-based linear structure having a network structure in the matrix. Since the metal-based linear structure having a network structure functions as a so-called conductive component and lowers the resistance value, the conductivity necessary for the conductive region appears. Since the non-conductive region does not have a metal-based linear structure or has a smaller abundance than the conductive region and does not have a network structure, it does not exhibit conductivity.
- a method for producing a patterned conductive layer includes a method of forming a non-conductive region by removing or reducing a metal-based linear structure in a part of a region after forming a conductive layer on the entire surface of the substrate, and screen printing, There is a method of directly forming a pattern of a conductive region by a technique such as offset gravure printing or inkjet.
- the present invention is preferably used in the former method for forming a non-conductive region after forming a conductive layer on the entire surface.
- a method of forming a conductive layer on the entire surface a method in which a metal-based linear structure is dispersed in the matrix described above, or a dispersion of the metal-based linear structure is applied and dried, and then a matrix solution is applied. And impregnating and curing.
- Coating methods for dispersions and matrix solutions of metallic linear structures are cast, spin coating, dip coating, bar coating, spraying, blade coating, slit die coating, gravure coating, reverse coating, screen printing, mold coating, and printing transfer. And general methods such as a wet coating method such as inkjet.
- each of the above methods can uniformly apply the dispersion liquid and is difficult to cause scratches on the substrate, or wet coating using a micro gravure that can form a conductive layer uniformly and with high productivity. The method is preferred.
- non-conductive regions that is, removal or reduction of metal-based linear structures, chemical etching methods that use metal etchant or etching paste to disconnect and remove metal-based linear structures, and metal ablation by laser ablation Examples of the method include disconnection and disappearance of the structure.
- the chemical etching method is preferable because the inorganic particles can be dissolved simultaneously with etching the metal-based linear structure, and the patterning and the process of generating voids in the non-conductive layer can be performed in the same process. Used for.
- the conductive laminate according to the present invention is preferably a transparent conductive laminate having a total light transmittance of 80% or more based on JIS K7361-1 (1997) when incident from the conductive layer side.
- the touch panel incorporated as the conductive laminate of the present invention exhibits excellent transparency and can clearly recognize the display on the display provided on the lower layer of the touch panel using the transparent conductive laminate.
- the transparency in the present invention means that the total light transmittance based on JIS K7361-1 (1997) when incident from the conductive layer side is 80% or more, preferably 85% or more, more Preferably it is 90% or more.
- the surface opposite to the conductive side (the side on which the conductive layer is laminated in the present invention) with respect to the base material is provided with wear resistance, high surface hardness, solvent resistance, stain resistance, etc.
- the provided hard coat treatment may be performed.
- the surface resistance value on the conductive layer side is preferably 1 ⁇ 10 1 ⁇ / ⁇ or more and 1 ⁇ 10 4 ⁇ / ⁇ or less, more preferably 1 ⁇ 10 1 ⁇ / ⁇ . ⁇ or more and 1.5 ⁇ 10 3 ⁇ / ⁇ or less.
- it can be preferably used as a conductive laminate for a touch panel. That is, if it is 1 ⁇ 10 1 ⁇ / ⁇ or more, the power consumption can be reduced, and if it is 1 ⁇ 10 4 ⁇ / ⁇ or less, the influence of errors in the coordinate reading of the touch panel can be reduced.
- additives can be added to the base material and / or the conductive layer used in the present invention within a range not impairing the effects of the present invention.
- the additives include organic fine particles, crosslinking agents, flame retardants, flame retardant aids, heat stabilizers, oxidation stabilizers, leveling agents, slip activators, antistatic agents, ultraviolet absorbers, and light stabilizers.
- Nucleating agents, dyes, fillers, dispersants, coupling agents and the like can be used.
- two or more patterned conductor layers of the present invention can be used by being laminated. When two or more layers are stacked, they are bonded and stacked by a bonding layer.
- a bonding layer an adhesive or a pressure-sensitive adhesive can be used, and a pressure-sensitive adhesive is preferably used from the viewpoints of handleability and flexibility.
- an acrylic pressure-sensitive adhesive, a silicone-based pressure-sensitive adhesive, a urethane-based pressure-sensitive adhesive, and the like can be used.
- an acrylic pressure-sensitive adhesive is preferably used because it is easy to adjust the adhesive properties and color tone.
- the conductive laminate and / or the patterned conductive laminate of the present invention can be preferably used for a display body, and can be preferably used for a touch panel and electronic paper.
- a schematic cross-sectional view showing an example of a touch panel is shown in FIG.
- the touch panel is one in which the conductive laminate (for example, FIG. 1) of the present invention in which a conductive layer having a network structure made of a metal-based linear structure is laminated is mounted alone or in combination with other members. Examples thereof include a resistive touch panel and a capacitive touch panel.
- the conductive layer of the conductive laminate of the present invention includes a metal-based linear structure (any or more) as indicated by reference numerals 12, 13, 14, and 15 as shown in FIG.
- the touch panel on which the conductive laminate of the present invention is mounted is formed by joining and laminating a conductive laminate 19 with a joining layer 22 such as an adhesive or a pressure sensitive adhesive as shown in FIG.
- a hard coat layer 24 laminated on the screen side base material and the screen side base material of the touch panel is provided.
- Such a touch panel is used, for example, by attaching a lead wire and a drive unit, etc., and incorporating it on the front surface of the liquid crystal display.
- the layer in which voids are present in the present invention can be disposed at any position in the patterned conductive laminate, but is preferably disposed between the substrate and the patterned conductive layer.
- the patterned conductive layer when the patterned conductive layer is provided only on one side of the substrate, it is preferable to have a layer in which a void exists between the substrate and the patterned conductive layer.
- a patterned conductive layer formed on both surfaces of the substrate may have a layer in which a void exists between any one of the patterned conductive layers and the substrate.
- the void of the present invention is generated when inorganic particles are dissolved or decomposed. Therefore, a void is present by forming a void by infiltrating a layer containing inorganic particles into an acid or alkaline solution, or applying energy from the outside by heating, laser, or the like.
- the process for forming a layer with voids as described above and the process for forming a non-conductive region in a conductive laminate are performed simultaneously, the number of steps is reduced and productivity is improved. It is preferably formed on the same surface as the layer.
- the layer in which voids are present is formed on the surface side of the patterned conductive layer, moisture and gas in the air easily pass through the layer, and the durability of the patterned conductive layer may be reduced. Therefore, the layer in which the void is present is preferably formed between the base material and the patterned conductive layer.
- the layer in which the void is present has a layer thickness sufficient to embed the void. Specifically, a layer thickness of 200 nm or more is desirable. When the layer thickness is less than 200 nm, voids are not formed in the layer, and the change in optical characteristics, which is the effect of the present invention, may not be obtained. In addition, as an upper limit of layer thickness, 1 micrometer or less is preferable from viewpoints, such as a softness
- composition of the layer in which voids are present a polymer having a crosslinked structure similar to that described in the above [Matrix] section can be suitably used.
- each of the conductive region (A) and non-conductive region (B) of the sample was scanned with a scanning transmission electron microscope (Hitachi Scanning Electron Microscope HD-2700, manufactured by Hitachi High-Technologies Corporation) or a field emission scanning electron microscope ( Using JSM-6700-F (manufactured by JEOL Ltd.), the acceleration voltage was 3.0 kV, the observation magnification and the contrast of the image were appropriately adjusted, and observation was performed at each magnification.
- a scanning transmission electron microscope Hitachi Scanning Electron Microscope HD-2700, manufactured by Hitachi High-Technologies Corporation
- JSM-6700-F manufactured by JEOL Ltd.
- VK-9700 / 9710 manufactured by Keyence Corporation observation application
- VK-H1V1 manufactured by Keyence Corporation shape analysis application
- VK-H1A1 included standard objective lens 10X (Nikon Corporation CF IC EPI Plan 10X), 20X (Nikon Corporation CF IC EPI Plan 20X), 50X (Nikon Corporation CF) IC EPI Plan Apo 50X), 150X (Nikon CF IC EPI Plan Apo 150X) was used to observe the same position on the conductive side at each magnification, and image analysis was performed from the image data.
- the conductive component was appropriately concentrated and diluted to prepare a sample. Subsequently, the component contained in a sample was specified using the following evaluation methods.
- the analysis method was performed by combining the following analysis methods, and those that can be measured with fewer combinations were preferentially applied.
- Nuclear magnetic resonance spectroscopy 1 H-NMR, 13 C-NMR, 29 Si-NMR, 19 F-NMR), two-dimensional nuclear magnetic resonance spectroscopy (2D-NMR), infrared spectrophotometry (IR), Raman Spectroscopy, mass spectrometry (gas chromatography-mass spectrometry (GC-MS), pyrolysis gas chromatography-mass spectrometry (pyrolysis GC-MS), matrix-assisted laser desorption ionization mass spectrometry (MALDI-MS) ), Time of Flight Mass Spectrometry (TOF-MS), Time of Flight Matrix Assisted Laser Desorption / Ionization Mass Spectrometry (MALDI-TOF-MS), Dynamic Secondary Ion Mass Spectrometry (Dynamic-SIMS), Time of Flight Type II Secondary ion mass spectrometry (TOF-SIMS), other static secondary ion mass spectrometry (Static-SIMS), etc.)
- a ring type probe (URS probe MCP-HTP14 manufactured by Mitsubishi Chemical Corporation) is connected and 100 mm ⁇ 100 mm in a double ring system. The central part of the sample was measured. An average value was calculated for three samples, and this was defined as a surface resistance value R 0 [ ⁇ / ⁇ ].
- Total light transmittance, haze A transparent adhesive on the PET film side of a 188 ⁇ m thick optical PET film having a hard coat layer (Forseed 423C manufactured by China Paint Co., Ltd.) formed on one side of the conductive layer side of the sample. Bonded with Nitto Denko's LUCIACS CS9621T) and using a turbidimeter (cloudiness meter) NDH2000 (manufactured by Nippon Denshoku Industries Co., Ltd.) based on JIS K 7361-1 (1997) The total light transmittance and haze in the thickness direction were measured by making light incident from the conductive layer side. Measurements were made on three samples, and the average value of the three samples was calculated and used as the total light transmittance and haze for each level. In this measurement, the value was obtained by rounding off the second digit.
- ⁇ L * 0 value a value obtained by performing the same diffuse reflection measurement on the patterned conductive laminate of the present invention having the same surface resistance value as that of the sample to be measured and containing no inorganic particles and / or voids was defined as ⁇ L * 0 value.
- This ⁇ L * 0 value varies depending on the abundance of the metal-based linear structure, that is, the surface resistance value of the conductive laminate. For example, when the amount of the metal-based linear structure is large and the surface resistance value is low, the ⁇ L * 0 value increases.
- An equivalent surface resistance value is an equivalent surface resistance value within a range of a certain value ⁇ 15 ⁇ / ⁇ .
- thermo-hygrostat PR-3SP manufactured by Tabai Espec Co., Ltd. operated at a temperature and humidity of 60 ° C and 90% RH, and taken out after 240 hours.
- the surface resistance value was measured.
- the change rate (unit:%) of the surface resistance value before and after the surface resistance value test was calculated by the following calculation formula.
- the surface resistance value was measured by the method described in (3) before and after the test.
- Metal-based linear structure Metal-based linear structure "silver nanowire” Silver nanowire (short axis: 50 to 100 nm, long axis: 20 to 40 ⁇ m) ⁇ Matrix and undercoat>
- Acrylic composition A An acrylic composition containing a compound having 3 or more carbon-carbon double bond groups contributing to the polymerization reaction as an acryloyl group (Flucure HC-6, manufactured by Soken Chemical Co., Ltd., solid content concentration 51 mass%). The cured product has a crosslinked structure.
- Photopolymerization initiator A -Photopolymerization initiator having a maximum absorption wavelength of 300 nm (Ciba IRGACURE (registered trademark) 907 manufactured by Ciba Japan Co., Ltd.).
- Photopolymerization initiator B Photopolymerization initiator having a maximum absorption wavelength of 320 nm (Ciba IRGACURE (registered trademark) 369, manufactured by Ciba Japan Co., Ltd.).
- Coating liquid A An aqueous dispersion in which an acrylic resin having the following copolymer composition is dispersed in water in the form of particles (so-called emulsion coating liquid and emulsion particle diameter is 50 nm) ⁇ Copolymerization component Methyl methacrylate 63% by mass Ethyl acrylate 35% by mass Acrylic acid 1% by mass N-methylolacrylamide 1% by mass (2) Coating liquid B Ammonium salt aqueous dispersion in which a polyester resin having the following copolymer composition is dispersed in water in the form of particles.
- Acid component Terephthalic acid 28 mol% Isophthalic acid 9 mol% Trimellitic acid 10 mol% Sebacic acid 3 mol% ⁇ Glycol component Ethylene glycol 15 mol% Neopentyl glycol 18 mol% 1,4-butanediol 17 mol%.
- Inorganic particles > Inorganic particles A Calcium carbonate fine particle surface-treated with fatty acid (Calflex C manufactured by New Lime Co., Ltd., primary average particle size 40 nm) Inorganic particles B Calcium carbonate dispersion (manufactured by Maruo Calcium Co., Ltd. NK-03, solid content concentration 20 mass% average particle size 300 nm) Inorganic particles C Calcium carbonate fine particle powder surface-treated with fatty acid (Viscal P, New Lime Co., Ltd., primary average particle diameter 150 nm).
- Example 1 Inorganic particles A5.0 g, ethyl acetate 95.0 g, 200.0 g of zirconia beads having an average particle diameter of 0.4 mm are mixed, and the number of shakes is 300 times / minute with a shaker SR-2DW (manufactured by Taitec Corporation). After shaking and dispersing under conditions for 2 hours, the zirconia beads were removed by filtration to obtain a dispersion of inorganic particles A.
- shaker SR-2DW manufactured by Taitec Corporation
- a silver nanowire dispersion (CleraOhm Ink-A AQ manufactured by Cambrios, USA) was prepared as an aqueous dispersion containing a metal-based linear structure.
- the silver nanowire dispersion liquid was diluted so that the concentration of silver nanowires was 0.054% by mass to prepare a silver nanowire dispersion coating liquid.
- This silver nanowire-dispersed coating liquid was applied onto the undercoat layer using a slit die coat equipped with a shim made of sus (sim thickness 50 ⁇ m), and dried at 120 ° C. for 2 minutes to form a conductive component. .
- the prepared matrix composition was applied using a slit die coat with shim (shim thickness 50 ⁇ m) attached to the conductive component-laminated side, dried at 120 ° C. for 2 minutes, and then irradiated with ultraviolet rays at 80 mJ / cm 2. Irradiated and cured to form a conductive layer having a matrix portion thickness of 120 nm to obtain a conductive laminate.
- shim shim thickness 50 ⁇ m
- This conductive laminate is a conductive laminate containing inorganic particles in the undercoat layer, and the inorganic particles are calcium carbonate and contain an amount of 10% by mass with respect to the undercoat layer.
- the average particle diameter of the inorganic particles was 152 nm. Further, the surface resistance value R 0 of this conductive laminate was 154.8 ⁇ / ⁇ .
- an etching solution containing 36% by mass hydrochloric acid: 60% by mass nitric acid: water at a mass ratio of 20: 3: 17 is heated to 45 ° C., and only half of the sample (50 mm ⁇ 50 mm range) is heated for 5 minutes. Etching was performed by dipping. As a result, a patterned conductive laminate sample in which the region immersed in the etching solution became a non-conductive region and the other region was a conductive region was obtained.
- the non-conductive region of this patterned conductive laminate contains voids having an average void diameter of 160 nm, the pattern is non-visible, and has a similar surface resistance value and does not contain inorganic particles and / or voids. The non-visibility of the pattern was improved as compared with the composite conductive laminate.
- Example 2 A conductive component was laminated on the base material by the same material and method as in Example 1.
- This conductive laminate is a conductive laminate containing inorganic particles in a matrix, and the inorganic particles are calcium carbonate and contain an amount of 10% by mass with respect to the matrix material.
- the average particle diameter of the inorganic particles was 145 nm.
- the surface resistance value R 0 of this conductive laminate was 156.0 ⁇ / ⁇ .
- a patterned conductive laminate sample was obtained in the same manner as in Example 1.
- the non-conductive region of this patterned conductive laminate includes voids having an average void diameter of 164 nm, the pattern is non-visible, and has a similar surface resistance value and does not contain inorganic particles and / or voids.
- the non-visibility of the pattern was improved as compared with the composite conductive laminate.
- Example 3 A dispersion of inorganic particles A was obtained in the same manner as in Example 1.
- Example 2 a conductive component and a matrix were formed in the same manner as in Example 1 on the opposite surface where the hard coat layer was formed, to obtain a conductive laminate.
- This conductive laminate is a conductive laminate containing inorganic particles in a hard coat layer formed on the side opposite to the conductive layer.
- the inorganic particles are calcium carbonate and contain an amount of 10% by mass with respect to the hard coat material.
- the average particle diameter of the inorganic particles was 149 nm. Further, the surface resistance value R 0 of this conductive laminate was 167.3 ⁇ / ⁇ .
- a patterned conductive laminate sample was obtained in the same manner as in Example 1.
- the non-conductive region of this patterned conductive laminate includes voids having an average void diameter of 151 nm, the pattern is non-visible, and has a similar surface resistance value and does not contain inorganic particles and / or voids.
- the non-visibility of the pattern was improved as compared with the composite conductive laminate.
- the layered structure of the patterned conductive laminate of this example is located on the opposite surface of the conductive laminate with the inorganic particles and / or voids interposed therebetween, there is a process of patterning both surfaces individually. It was necessary.
- Example 4 Undercoat material composition is acrylic composition A 53.5g, photopolymerization initiator A 1.29g, photopolymerization initiator B 1.29g, ethyl acetate 801.4g, inorganic particle A dispersion 150.0g, silver nanowire dispersion A conductive laminate was obtained in the same manner as in Example 1 except that the conditions for applying the liquid were adjusted so that the shim thickness was 75 ⁇ m and the wet film thickness was 1.5 times.
- This conductive laminate is a conductive laminate containing inorganic particles in the undercoat layer, and the inorganic particles are calcium carbonate and contained in an amount of 25% by mass with respect to the undercoat material.
- the average particle diameter of the inorganic particles was 154 nm.
- the surface resistance value R 0 of this conductive laminate was 50.3 ⁇ / ⁇ .
- a patterned conductive laminate was obtained in the same manner as in Example 1.
- the non-conductive region of this patterned conductive laminate contains voids having an average void diameter of 155 nm, the pattern is non-visible, and has a similar surface resistance value and does not contain inorganic particles and / or voids.
- the non-visibility of the pattern was improved as compared with the composite conductive laminate.
- Example 5 Same as Example 1, except that the undercoat material composition was 53.5 g of acrylic composition A, 1.29 g of photopolymerization initiator A, 1.29 g of photopolymerization initiator B, 931.9 g of ethyl acetate, and 15.0 g of inorganic particles B. A conductive laminate was obtained by this method.
- This conductive laminate is a conductive laminate containing inorganic particles in the undercoat layer, and the inorganic particles are calcium carbonate and contain an amount of 10% by mass with respect to the undercoat material.
- the average particle diameter of the inorganic particles was 284 nm. Further, the surface resistance value R 0 of this conductive laminate was 153.5 ⁇ / ⁇ .
- a patterned conductive laminate was obtained in the same manner as in Example 1.
- the non-conductive region of this patterned conductive laminate contained voids having an average void diameter of 303 nm and the pattern non-visibility did not reach a good level, but inorganic particles and / or voids with an equivalent surface resistance value. It was improved as compared with the patterned conductive laminate containing no.
- Example 6 (Example 6) Implemented except that the undercoat material composition was 53.5 g of acrylic composition A, 1.29 g of photopolymerization initiator A, 1.29 g of photopolymerization initiator B, 829.9 g of ethyl acetate, and 120.0 g of dispersion of inorganic particles A
- the undercoat material composition was 53.5 g of acrylic composition A, 1.29 g of photopolymerization initiator A, 1.29 g of photopolymerization initiator B, 829.9 g of ethyl acetate, and 120.0 g of dispersion of inorganic particles A
- a conductive laminate was obtained in the same manner as in Example 1.
- Example 7 (Example 7) Implemented except that the undercoat material composition was 53.5 g of acrylic composition A, 1.29 g of photopolymerization initiator A, 1.29 g of photopolymerization initiator B, 915.4 g of ethyl acetate, and 30.0 g of dispersion of inorganic particles A
- the undercoat material composition was 53.5 g of acrylic composition A, 1.29 g of photopolymerization initiator A, 1.29 g of photopolymerization initiator B, 915.4 g of ethyl acetate, and 30.0 g of dispersion of inorganic particles A
- a conductive laminate was obtained in the same manner as in Example 1.
- This conductive laminate is a conductive laminate including inorganic particles in the undercoat layer, and the inorganic particles are calcium carbonate and contained in an amount of 5% by mass with respect to the undercoat material.
- the average particle diameter of the inorganic particles was 161 nm.
- the surface resistance value R 0 of this conductive laminate was 144.2 ⁇ / ⁇ .
- a patterned conductive laminate was obtained in the same manner as in Example 1.
- the non-conductive region of this patterned conductive laminate contains voids with an average void diameter of 160 nm, and the pattern non-visibility has not reached a good level, but the inorganic particles and / or with the equivalent surface resistance value. Compared to patterned conductive laminates that do not contain voids.
- Example 8 A conductive laminate was obtained in the same manner as in Example 1 except that the conditions for applying the silver nanowire dispersion were adjusted so that the shim thickness was 75 ⁇ m and the wet film thickness was 1.5 times.
- This conductive laminate is a conductive laminate containing inorganic particles in the undercoat layer, and the inorganic particles are calcium carbonate and contain an amount of 10% by mass with respect to the undercoat material.
- the average particle size of the inorganic particles was 144 nm. Further, the surface resistance value R 0 of this conductive laminate was 50.8 ⁇ / ⁇ .
- a patterned conductive laminate was obtained in the same manner as in Example 1.
- the non-conductive region of this patterned conductive laminate contains voids with an average void diameter of 152 nm, and the pattern non-visibility has not reached a good level, but the inorganic particles and / or with the equivalent surface resistance value. Compared to patterned conductive laminates that do not contain voids.
- Example 9 Inorganic particles A5.0 g and ethyl acetate 95.0 g were mixed, and dispersed by vibration for 2 hours with an ultrasonic cleaner US-2R (manufactured by ASONE Co., Ltd.) under the condition of an output of 160 W to obtain a dispersion of inorganic particles A.
- a conductive laminate was obtained in the same manner as in Example 1 except that.
- This conductive laminate is a conductive laminate containing inorganic particles in the undercoat layer, and the inorganic particles are calcium carbonate and contain an amount of 10% by mass with respect to the undercoat material.
- the average particle diameter of the inorganic particles was 641 nm.
- the surface resistance value R 0 of this conductive laminate was 163.3 ⁇ / ⁇ .
- a patterned conductive laminate was obtained in the same manner as in Example 1.
- the non-conductive region of this patterned conductive laminate contains voids with an average void diameter of 711 nm, and the pattern non-visibility has not reached a good level, but the inorganic particles and / or with the same surface resistance value. Compared to patterned conductive laminates that do not contain voids. Further, the patterned conductive layer body showed an increase in haze value.
- Example 10 Inorganic particles C 10.0 g, water 54.0 g, isopropyl alcohol 36.0 g, zirconia beads 200.0 g having an average particle diameter of 0.4 mm are mixed, and the number of times of shaking with a shaker SR-2DW (manufactured by Taitec Co., Ltd.) After shaking and dispersing at 300 times / minute for 2 hours, the zirconia beads were removed by filtration to obtain a dispersion of inorganic particles C.
- a shaker SR-2DW manufactured by Taitec Co., Ltd.
- PET pellets Extreme viscosity 0.63 dl / g that do not contain externally added particles are sufficiently vacuum-dried, then supplied to an extruder, melted at 285 ° C., extruded into a sheet form from a T-shaped die, It was wound around a mirror-casting drum having a surface temperature of 25 ° C. using an electric application casting method and cooled and solidified. This unstretched film was heated to 90 ° C. and stretched 3.4 times in the longitudinal direction to obtain a uniaxially stretched film. One side of this film was subjected to corona discharge treatment in air.
- the mixture obtained in (1) was used as an easy-adhesion layer coating solution and applied to the corona discharge treated surface of the uniaxially stretched film.
- the uniaxially stretched film coated with the easy-adhesion layer coating liquid is gripped with a clip and guided to a preheating zone, dried at an ambient temperature of 75 ° C., raised to 110 ° C. using a radiation heater, and dried again at 90 ° C., Subsequently, the film was continuously stretched 3.5 times in the width direction in a heating zone at 120 ° C., and then heat-treated in a heating zone at 220 ° C. for 20 seconds to produce a crystallized laminated film as a base film. At this time, the thickness of the base film was 125 ⁇ m, and the thickness of the easy adhesion layer was 350 nm.
- This conductive laminate is a conductive laminate containing inorganic particles in the easy-adhesion layer, and the inorganic particles are calcium carbonate and contained 7.7% by mass with respect to the easy-adhesion layer composition.
- the average particle diameter of the inorganic particles was 155 nm.
- the surface resistance value R 0 of this conductive laminate was 53.0 ⁇ / ⁇ .
- a patterned conductive laminate was obtained in the same manner as in Example 1.
- the non-conductive region of this patterned conductive laminate contains voids having an average void diameter of 161 nm, and the non-visibility of the pattern has not reached a good level. Compared to patterned conductive laminates that do not contain voids.
- Example 1 A conductive laminate in the same manner as in Example 1 except that the undercoat material composition was 53.5 g of acrylic composition A, 1.29 g of photopolymerization initiator A, 1.29 g of photopolymerization initiator B, and 943.9 g of ethyl acetate. Got.
- This conductive laminate does not contain inorganic particles in any layer.
- the surface resistance value R 0 of this conductive laminate was 152.7 ⁇ / ⁇ .
- Example 2 a patterned conductive laminate was obtained in the same manner as in Example 1.
- the non-conductive region of this patterned conductive laminate did not contain voids in any layer, and the pattern non-visibility was low.
- Comparative Example 2 A conductive laminate was obtained in the same manner as in Comparative Example 1 except that the conditions for applying the silver nanowire dispersion were adjusted so that the shim thickness was 75 ⁇ m and the wet film thickness was 1.5 times.
- This conductive laminate does not contain inorganic particles in any layer.
- the surface resistance value R 0 of this conductive laminate was 53.8 ⁇ / ⁇ .
- Example 2 a patterned conductive laminate was obtained in the same manner as in Example 1.
- the non-conductive region of this patterned conductive laminate did not contain voids in any layer, and the pattern non-visibility was low.
- the conductive laminate and the patterned conductive laminate of the present invention are suitably used for display body applications such as touch panels, liquid crystal displays, and electronic papers because of their good pattern non-visibility.
- Base material 2 Conductive layer 3: Metal-based linear structure 4: Inorganic particles 5: Void 6: Matrix 7: Undercoat layer 8: Conductive region 9: Nonconductive region 10: Back surface hard coat layer 11: Laminated surface Conductive surface 12 observed from the direction perpendicular to the surface: single fibrous conductor 13: aggregate of fibrous conductors 14: nanowire 15: acicular conductor 16: contact 17 formed by overlapping of fibrous conductors : Contact 18 formed by overlapping nanowires 18: contact formed by overlapping needle-like conductors 19: conductive laminate 20: base material of conductive laminate 21: conductive layer 22 of conductive laminate: stacking conductive laminate Bonding layer 23: screen side substrate 24: hard coat layer 25: easy adhesion layer
Abstract
Description
(1)基材の少なくとも片面に導電層を有する導電積層体であって、該導電層はネットワーク構造を持つ金属系線状構造体を含み、さらに導電積層体のいずれかの層に無機粒子を含んでいることを特徴とする導電積層体。
(2)基材と導電層との間に無機粒子を含む層を有することを特徴とする(1)記載の導電積層体。
(3)基材の少なくとも片面にパターン化導電層を有するパターン化導電積層体であって、該パターン化導電層はネットワーク構造を持つ金属系線状構造体が存在する導電領域と、ネットワーク構造を持つ金属系線状構造体が存在しない非導電領域を有し、さらに非導電領域の積層構成のいずれかの層にボイドが存在することを特徴とするパターン化導電積層体。
(4)基材とパターン化導電層との間にボイドが存在する層を有することを特徴とする(3)記載のパターン化導電積層体。
(5)導電領域よりも非導電領域に多くのボイドが存在することを特徴とする前記(4)に記載のパターン化導電積層体。
(6)前記(3)、(4)、(5)のいずれかに記載のパターン化導電積層体の製造方法であって、(1)または(2)に記載の導電積層体の無機粒子を薬液処理で溶解することによりボイドを形成することを特徴とするパターン化導電積層体の製造方法。
(7)薬液処理で、無機粒子を溶解することによりボイドを形成すると同時に、ネットワーク構造を持つ金属系線状構造体をも除去し、非導電領域を形成することを特徴とする前記(6)に記載のパターン化導電積層体の製造方法。
(8)前記(6)または(7)に記載のパターン化導電積層体の製造方法で得られるパターン化導電積層体。
(9)金属系線状構造体が、銀ナノワイヤーである前記(1)に記載の導電積層体。
(10)無機粒子の平均粒子径が500nm以下であることを特徴とする前記(1)に記載の導電積層体。
(11)非導電領域に含まれるボイドの平均ボイド径が500nm以下であることを特徴とする前記(3)、(4)、(5)、(8)のいずれかに記載のパターン化導電積層体。
(12)無機粒子が炭酸塩であることを特徴とする前記(1)に記載の導電積層体。
(13)前記(1)に記載の導電積層体、または、前記(3)、(4)、(5)、(8)のいずれかに記載のパターン化導電積層体を用いた表示体。
(14)前記(13)に記載の表示体を用いたタッチパネル。
(15)前記(13)に記載の表示体を用いた電子ペーパー。
本発明の導電積層体は、基材の少なくとも片面に導電層を有する。すなわち、基材の片面にのみ導電層を有していてもよいし、基材の両面に導電層を有していてもよい。導電層は、金属系線状構造体からなるネットワーク構造を有する導電成分が、架橋構造を有する高分子からなるマトリックス中に含有されてなるものである。金属系線状構造体からなるネットワーク構造を有する導電成分がランダムな配向であると、導電性および耐久性に加えて良好な光学特性をも得ることができるので、本発明の導電積層体を用いた表示体は表示画像が鮮明なものとなるので好ましい。導電積層体には、必要に応じてハードコート層やアンダーコート層などの各種機能性層を付与することもできる。ハードコート層は導電積層体の導電層を形成している側の最表層、もしくは基材を挟んで反対側の最表層に設けることができる。ハードコート層は主に表面強度や防汚性、耐指紋性などを向上する為に設けられ、さらに表面に微細な凹凸を形成し防眩性を付与することもできる。ハードコート層としては、硬化した際の透明性、硬度などの特性が優れる点から熱硬化型、紫外線硬化型のアクリル系樹脂が好適に用いられる。アンダーコート層は基材と導電層との間に設けられ、主に基材と導電層との密着性を向上する目的で設けられる。アンダーコート層は基材、導電層との密着性、透明性の点から熱硬化型あるいは紫外線硬化型のポリエステル系樹脂やアクリル系樹脂が好適に用いられる。本発明の導電積層体は前記いずれかの層に後述する無機粒子を含んでいればパターン化後にパターンの非視認性が良好となる効果を発現できる。また、導電層あるいはアンダーコート層に無機粒子を含んでいると、ケミカルエッチング法を採用した際に導電層のパターン化と同時にパターンの非視認性が良好となる効果を発現するため、工程数の減少による製造コスト削減の観点から導電層および/またはアンダーコート層に無機粒子を含んでいることが望ましい。
本発明の導電積層体における基材の素材として、具体的には例えば透明な樹脂、ガラスなどを挙げることができる。樹脂としては、ポリエチレンテレフタレート(PET)、ポリエチレンナフタレート(PEN)などのポリエステル、ポリアミド、ポリイミド、ポリフェニレンスルフィド、アラミド、ポリエチレン、ポリプロピレン、ポリスチレン、ポリ乳酸、ポリ塩化ビニル、ポリカーボネート、ポリメタクリル酸メチル等のアクリル系・メタクリル系樹脂、脂環式アクリル樹脂、シクロオレフィン樹脂、トリアセチルセルロース、アクリロニトリルブタジエンスチレン共重合合成樹脂(ABS)、ポリ酢酸ビニル、メラミン系樹脂、フェノール系樹脂、ポリ塩化ビニルやポリ塩化ビニリデン等の塩素原子(Cl原子)を含有する樹脂、フッ素原子(F原子)を含有する樹脂、シリコーン系樹脂及びこれら樹脂の混合及び/又は共重合したものが挙げられ、ガラスとしては、通常のソーダガラスを用いることができる。また、これらの複数の基材を組み合わせて用いることもできる。例えば、樹脂とガラスを組み合わせた基材、2種以上の樹脂を積層した基材などの複合基材であってもよい。基材の形状については、厚み250μm以下で巻き取り可能なフィルムであっても、厚み250μmを超える基板であっても後に述べる全光線透過率の範囲で有ればよい。コスト、生産性、取り扱い性等の観点からは250μm以下の樹脂フィルムが好ましく、より好ましくは190μm以下、さらに好ましくは150μm以下、特に好ましくは100μm以下の樹脂フィルムである。基材として樹脂フィルムを用いる場合、樹脂を未延伸、一軸延伸、二軸延伸してフィルムとしたものを適用することができる。これら樹脂フィルムのうち、基材への成形性、透明性等の光学特性、生産性等の観点から、ポリエチレンテレフタレート(PET)、ポリエチレンナフタレート(PEN)などのポリエステルフィルム、またPENとの混合及び/又は共重合したPETフィルム、ポリプロピレンフィルムを好ましく使用することができる。なお、基材に用いる樹脂フィルムは片面または両面に易接着層が設けられた易接着フィルムであってもよい。
本発明における金属系線状構造体としては、例えば、繊維状導電体、ナノワイヤー、ウィスカーやナノロッドのような針状導電体等が挙げられる。なお、繊維状とは、アスペクト比=長軸の長さ(金属系線状構造体の長さ)/短軸の長さ(金属系線状構造体の直径)が10より大きいことをいう。形状については特に限定されず、直線状であっても曲線状であってもよく、その一部に直線部および/または曲線部を有する形状であってもよい。ナノワイヤーとは、図7における符号14に例示するような、弧の形状をしている構造体であり、針状とは、例えば図7における符号15に例示するような、直線形状をしている構造体である。なお、金属系線状構造体は、単独で存在する場合の他に、集合体を形成して存在する場合がある。集合体については、例えば金属系線状構造体の配置の方向性に規則性がなくランダムに集合した状態であっても良く、また金属系線状構造体の長軸方向の面同士が平行に集合した状態であっても良い。長軸方向の面同士が平行に集合した状態の例としては、バンドルという集合体となることが知られており、金属系線状構造体が類似のバンドル構造を有していても良い。本発明において好ましく用いられる金属系線状構造体は金属ナノワイヤーであり、金属ナノワイヤーの金属組成としては特に制限は無く、貴金属元素、貴金属酸化物や卑金属元素の1種または複数の金属から構成されることができるが、貴金属(例えば、金、白金、銀、パラジウム、ロジウム、イリジウム、ルテニウム、オスミウム等)及び鉄、コバルト、銅、錫からなる群に属する少なくとも1種の金属を含むことが好ましく、導電性の観点から少なくとも銀を含むことがより好ましい。金属系線状構造体として用いることのできる貴金属や貴金属酸化物のナノワイヤーは、特表2009-505358号公報、特開2009-129607号公報、特開2009-070660号公報に記載されており、また金属酸化物のウィスカーや繊維状のような針状結晶としては、例えば、チタン酸カリウム繊維とスズ及びアンチモン系酸化物の複合酸化物であるデントールWKシリーズ(大塚化学(株)製)のWK200B、WK300R、WK500が市販されている。
本発明においてネットワーク構造とは、導電層内の個別の金属系線状構造体について見たとき、別の金属系線状構造体との接点の数の平均が少なくとも1を超えるような、分散構造を有することをいう。このとき接点は金属系線状構造体のいかなる部分間に形成されていてもよく、金属系線状構造体の末端部同士が接していたり、末端と金属系線状構造体の末端以外の部分が接していたり、金属系線状構造体の末端以外の部分同士が接していてもよい。ここで、接するとはその接点が接合していても、単に接触しているだけでもよい。なお、導電層中の金属系線状構造体のうち、ネットワークの形成に寄与していない(すなわち接点が0で、ネットワークとは独立して存在している)金属系線状構造体が一部存在していてもよい。
本発明における導電層には、前記金属系線状構造体を架橋構造を有する高分子からなるマトリックス中に含むことが好ましい。
本発明における導電積層体はそのいずれかの層中に無機粒子を含むことが好ましい。層中の無機粒子が薬液処理により溶解してボイドを発生することにより光学特性が変化する効果を発揮する。
本発明におけるパターン化導電層体は非導電領域のいずれかの層にボイドを含む。該ボイドは非導電領域に透過ヘイズ値の減少および拡散反射光を減少させる効果を発現する。非導電領域においては導電領域よりも金属系線状構造体が少ないことに起因して透過ヘイズ値および拡散反射光が減少するが、本発明では前述のような光学特性の差違を小さくすることでパターンの非視認性が向上したパターン化導電層体を得ることができる。
本発明における無機粒子を含む層は導電積層体中の任意の位置に配置することができる。例えば、基材と導電層との間にアンダーコート層として配置したり、導電層とは反対面にハードコート層として配置したりすることもできる。
本発明のパターン化導電積層体は、基材の少なくとも片側に、パターン化導電層を有する。
本発明におけるボイドが存在する層はパターン化導電積層体中の任意の位置に配置することができるが、基材とパターン化導電層との間に配置されることが好ましい。
[評価方法]
まず、各実施例および比較例における評価方法を説明する。
絶縁抵抗計(三和電気計器(株)製、DG6)を用いて、サンプルの各面に探針をあて、通電の有無からサンプルの導電面を特定する。
サンプルから導電層を剥離し、溶解する溶剤に溶解させた。必要に応じ、シリカゲルカラムクロマトグラフィー、ゲル浸透クロマトグラフィー、液体高速クロマトグラフィー等に代表される一般的なクロマトグラフィー等を適用し、それぞれ単一物質に分離精製して、以下の定性分析に供した。
導電積層体の導電層側の表面抵抗値を、非接触式抵抗率計(ナプソン(株)製 NC-10)を用い渦電流方式で100mm×50mmのサンプルの中央部分を測定した。3サンプルについて平均値を算出し、これを表面抵抗値R0[Ω/□]とした。検出限界を超えて表面抵抗値が得られなかった場合は、次いで以下の方法にて測定した。
サンプルの導電層側にハードコート層(中国塗料(株)製フォルシード423C)が片面に形成された厚み188μmの光学PETフィルムのPETフィルム側を透明粘着剤(日東電工(株)製LUCIACS CS9621T)で貼り合わせ、濁度計(曇り度計)NDH2000(日本電色工業(株)製)を用いてJIS K7361-1(1997年)に基づいて、導電積層体厚み方向の全光線透過率、ヘイズを導電層側から光を入射させて測定した。3サンプルについて測定し、3サンプルの平均値を算出し、これを各水準の全光線透過率、ヘイズとした。本測定に当たっては、2桁目を四捨五入して値を求めた。
サンプルの導電層側に、ハードコート層(中国塗料(株)製フォルシード423C)が片面に形成された厚み188μmの光学PETフィルムのPETフィルム側を透明粘着剤(日東電工(株)製LUCIACS CS9621T)で貼り合わせ、分光測色計CM-2600d(コニカミノルタセンシング(株)製)を用いて導電層側の反射光を測定した。拡散反射光の指標としてSCE方式でのL*a*b*表色系のL*値を採用した。測定は導電領域と非導電領域の両方でそれぞれ行い、各々のL*値の差であるΔL*値を求めた。
前述の拡散反射光測定におけるΔL*値が0.7以下となった場合、パターンの非視認性が良好と判断した。また、測定するサンプルと同等の表面抵抗値で本発明の無機粒子および/またはボイドを含まないパターン化導電積層体において同様の拡散反射光測定を行った値をΔL* 0値とした。このΔL* 0値は金属系線状構造体の存在量すなわち、導電積層体の表面抵抗値により変化する。例えば、金属系線状構造体の存在量が多く、表面抵抗値が低い場合はΔL* 0値は大きくなる。ここで、同等の表面抵抗値でΔL*-ΔL* 0≦-0.3の場合、パターンの非視認性は改善していると判断し、ΔL*-ΔL* 0>-0.3の場合、パターンの非視認性は改善されておらず、不良とした。尚、同等の表面抵抗値とは、ある値±15Ω/□の範囲内であれば、同等の表面抵抗値とする。
いずれの層にも無機粒子を含まない表面抵抗値140.1Ω/□、150.5Ω/□、162.0Ω/□、51.0Ω/□の4種類の導電積層体を用意した。これらをパターニングし得られたパターン化導電積層体のΔL*はそれぞれ1.93、1.96、2.02、3.27であり、それぞれの値をその表面抵抗値でのΔL* 0とした。このときの導電積層体およびパターン化導電積層体は後記する比較例1および2と同様の方法で得た。
100mm×50mmに切り出したサンプルを温湿度条件60℃90%RHで運転した恒温恒湿器(タバイエスペック(株)製PR-3SP)に投入し、240時間後に取り出して表面抵抗値を測定した。以下の計算式により、表面抵抗値試験前後での表面抵抗値の変化率(単位:%)を算出した。なお、表面抵抗値の測定は試験前後とも(3)記載の方法で実施した。
(試験後のサンプルの表面抵抗値/試験前のサンプルの表面抵抗値)×100(%)・・・(式)
[材料]
<基材>
厚み125μmのポリエチレンテレフタレートフィルム(東レ(株)製 “ルミラー”(登録商標)U48)を使用した。
金属系線状構造体「銀ナノワイヤー」
銀ナノワイヤー(短軸:50~100nm、長軸:20~40μm)
<マトリックスおよびアンダーコート>
(1)アクリル系組成物A
アクリロイル基として重合反応に寄与する炭素-炭素二重結合基を3個以上有する化合物を含有するアクリル系組成物(綜研化学(株)製 フルキュアHC-6、固形分濃度51質量%)。硬化物は、架橋構造を有する。
・極大吸収波長300nmの光重合開始剤(チバ・ジャパン(株)製 Ciba IRGACURE(登録商標)907)。
・極大吸収波長320nmの光重合開始剤(チバ・ジャパン(株)製 Ciba IRGACURE(登録商標)369)。
(1)塗液A
下記の共重合組成からなるアクリル樹脂を粒子状に水に分散させた水性分散液(いわゆる、エマルジョン塗液でエマルジョン粒子径は50nm)
・共重合成分
メチルメタクリレート 63質量%
エチルアクリレート 35質量%
アクリル酸 1質量%
N-メチロールアクリルアミド 1質量%
(2)塗液B
下記の共重合組成からなるポリエステル樹脂を粒子状に水に分散させたアンモニウム塩型の水性分散液
・酸成分
テレフタル酸 28モル%
イソフタル酸 9モル%
トリメリット酸 10モル%
セバシン酸 3モル%
・グリコール成分
エチレングリコール 15モル%
ネオペンチルグリコール 18モル%
1,4-ブタンジオール 17モル%。
無機粒子A
脂肪酸で表面処理した炭酸カルシウム微粒子粉末(ニューライム(株)製 カルフレックスC、一次平均粒子径40nm)
無機粒子B
炭酸カルシウム分散体(丸尾カルシウム(株)製 NK-03、固形分濃度20質量%平均粒子径300nm)
無機粒子C
脂肪酸で表面処理した炭酸カルシウム微粒子粉末(ニューライム(株)製 ヴィスカルP、一次平均粒子径150nm)。
無機粒子A5.0g、酢酸エチル95.0g、平均粒子径0.4mmのジルコニアビーズ200.0gを混合し、振とう機SR-2DW(タイテック(株)製)で振とう回数300回/分の条件で2時間振とう分散させた後、ジルコニアビーズを濾過により除去し無機粒子Aの分散体を得た。
実施例1と同様の材料、方法で基材に導電成分を積層形成した。
調製したマトリックス組成物を、導電成分を積層した側に、材質がsusのシム(シム厚み50μm)を装着したスリットダイコートを使用して塗布、120℃で2分間乾燥後、紫外線を80mJ/cm2照射し硬化させ、マトリックス部分の厚みが600nmである導電層を形成し、導電積層体を得た。
実施例1と同様の方法で無機粒子Aの分散体を得た。
アンダーコート材料組成をアクリル系組成物A53.5g、光重合開始剤A1.29g、光重合開始剤B1.29g、酢酸エチル801.4g、無機粒子Aの分散体150.0gとし、銀ナノワイヤー分散液を塗布する際の条件をシム厚み75μmとしてwet膜厚が1.5倍となるように調整した以外は実施例1と同様の方法で導電積層体を得た。
アンダーコート材料組成をアクリル系組成物A53.5g、光重合開始剤A1.29g、光重合開始剤B1.29g、酢酸エチル931.9g、無機粒子B15.0gとしたこと以外は実施例1と同様の方法で導電積層体を得た。
アンダーコート材料組成をアクリル系組成物A53.5g、光重合開始剤A1.29g、光重合開始剤B1.29g、酢酸エチル829.9g、無機粒子Aの分散体120.0gとしたこと以外は実施例1と同様の方法で導電積層体を得た。
続いて実施例1と同様の方法でパターン化導電積層体を得た。このパターン化導電積層体の非導電領域は平均ボイド径156nmのボイドを含んでおりパターンの非視認性は良好な水準には達していなかったが、同等の表面抵抗値で無機粒子および/またはボイドを含まないパターン化導電積層体と比較して改善されていた。
アンダーコート材料組成をアクリル系組成物A53.5g、光重合開始剤A1.29g、光重合開始剤B1.29g、酢酸エチル915.4g、無機粒子Aの分散体30.0gとしたこと以外は実施例1と同様の方法で導電積層体を得た。
銀ナノワイヤー分散液を塗布する際の条件をシム厚み75μmとしてwet膜厚が1.5倍となるように調整した以外は実施例1と同様の方法で導電積層体を得た。
無機粒子A5.0g、酢酸エチル95.0gを混合し、超音波洗浄機US-2R(アズワン(株)製)で出力160Wの条件で2時間振動分散させ、無機粒子Aの分散体を得たこと以外は実施例1と同様の方法で導電積層体を得た。
無機粒子C10.0g、水54.0g、イソプロピルアルコール36.0g、平均粒子径0.4mmのジルコニアビーズ200.0gを混合し、振とう機SR-2DW(タイテック(株)製)で振とう回数300回/分の条件で2時間振とう分散させた後、ジルコニアビーズを濾過により除去し無機粒子Cの分散体を得た。
アンダーコート材料組成をアクリル系組成物A53.5g、光重合開始剤A1.29g、光重合開始剤B1.29g、酢酸エチル943.9gとしたこと以外は実施例1と同様の方法で導電積層体を得た。
銀ナノワイヤー分散液を塗布する際の条件をシム厚み75μmとしてwet膜厚が1.5倍となるように調整した以外は比較例1と同様の方法で導電積層体を得た。
2:導電層
3:金属系線状構造体
4:無機粒子
5:ボイド
6:マトリックス
7:アンダーコート層
8:導電領域
9:非導電領域
10:裏面ハードコート層
11:積層面に垂直な方向より観察した導電面
12:単一の繊維状導電体
13:繊維状導電体の集合体
14:ナノワイヤー
15:針状導電体
16:繊維状導電体の重なりによって形成した接点
17:ナノワイヤーの重なりによって形成した接点
18:針状導電体の重なりによって形成した接点
19:導電積層体
20:導電積層体の基材
21:導電積層体の導電層
22:導電積層体を積層するための接合層
23:画面側の基材
24:ハードコート層
25:易接着層
Claims (15)
- 基材の少なくとも片面に導電層を有する導電積層体であって、該導電層はネットワーク構造を持つ金属系線状構造体を含み、さらに導電積層体のいずれかの層に無機粒子を含んでいることを特徴とする導電積層体。
- 基材と導電層との間に無機粒子を含む層を有することを特徴とする請求項1記載の導電積層体。
- 基材の少なくとも片面にパターン化導電層を有するパターン化導電積層体であって、該パターン化導電層はネットワーク構造を持つ金属系線状構造体が存在する導電領域と、ネットワーク構造を持つ金属系線状構造体が存在しない非導電領域を有し、さらに非導電領域の積層構成のいずれかの層にボイドが存在することを特徴とするパターン化導電積層体。
- 基材とパターン化導電層との間にボイドが存在する層を有することを特徴とする請求項3記載のパターン化導電積層体。
- 導電領域よりも非導電領域に多くのボイドが存在することを特徴とする請求項4に記載のパターン化導電積層体。
- 請求項3、4、5のいずれかに記載のパターン化導電積層体の製造方法であって、請求項1または2に記載の導電積層体の無機粒子を薬液処理で溶解することによりボイドを形成することを特徴とするパターン化導電積層体の製造方法。
- 薬液処理で、無機粒子を溶解することによりボイドを形成すると同時に、ネットワーク構造を持つ金属系線状構造体をも除去し、非導電領域を形成することを特徴とする請求項6に記載のパターン化導電積層体の製造方法。
- 請求項6または7に記載のパターン化導電積層体の製造方法で得られるパターン化導電積層体。
- 金属系線状構造体が、銀ナノワイヤーである請求項1に記載の導電積層体。
- 無機粒子の平均粒子径が500nm以下であることを特徴とする請求項1に記載の導電積層体。
- 非導電領域に含まれるボイドの平均ボイド径が500nm以下であることを特徴とする請求項3、4、5、8のいずれかに記載のパターン化導電積層体。
- 無機粒子が炭酸塩であることを特徴とする請求項1に記載の導電積層体。
- 請求項1に記載の導電積層体、または、請求項3、4、5、8のいずれかに記載のパターン化導電積層体を用いた表示体。
- 請求項13に記載の表示体を用いたタッチパネル。
- 請求項13に記載の表示体を用いた電子ペーパー。
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