JPWO2014010270A1 - Conductive laminate, patterned conductive laminate, method for producing the same, and touch panel using the same - Google Patents

Abstract

The present invention is intended to provide a patterned conductive laminate having good pattern non-visibility. A conductive laminate having a conductive layer on at least one side of a substrate, the conductive layer including a metal-based linear structure having a network structure, and further including inorganic particles in any one of the conductive layer bodies It is the conductive laminated body characterized by having.

Description

  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.

  2. Description of the Related Art In recent years, with respect to conductive members for electrodes in displays such as touch panels, liquid crystal displays, organic electroluminescence, electronic paper, 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.

  There is a conductive member with a conductive layer laminated on a substrate, and the conductive layer 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. The thing using an ingredient is proposed. For example, 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). Moreover, the electrically conductive laminated body which disperse | distributed metal nanowire in the matrix of the high curing degree using a polyfunctional component is proposed (patent document 2). Furthermore, 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).

  In addition, when applying these conductive members to a touch panel or the like, it is necessary to form a wiring pattern. As a pattern forming method, a chemical etching method using a photoresist or an etching solution is generally used. (Patent Document 4).

Special table 2010-507199 JP 2011-29037 A JP 2010-140859 A JP 2001-307567 A

  However, 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). As means for improving the invisibility of this pattern, 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. Although 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. In addition, 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.

  In view of the problems of the prior art, the present invention is intended to obtain a patterned conductive laminate having high non-visibility of a pattern portion.

In order to solve this problem, 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.
(3) A patterned conductive laminate having a patterned conductive layer on at least one side of a substrate, the patterned conductive layer having a conductive region where a metal-based linear structure having a network structure exists, and a network structure A patterned conductive laminate having a non-conductive region having no metal-based linear structure and having voids in any layer of the laminated structure of the non-conductive region.
(4) The patterned conductive laminate according to (3), which has a layer in which a void exists between the substrate and the patterned conductive layer.
(5) The patterned conductive laminate according to (4), wherein more voids are present in the nonconductive region than in the conductive region.
(6) The method for producing a patterned conductive laminate according to any one of (3), (4), and (5), wherein the inorganic particles of the conductive laminate according to (1) or (2) are used. A method for producing a patterned conductive laminate, wherein a void is formed by dissolution by chemical treatment.
(7) In the above (6), the void is formed by dissolving the inorganic particles in the chemical treatment, and at the same time, the metal-based linear structure having a network structure is removed to form a non-conductive region. The manufacturing method of the patterned conductive laminated body as described in any one of.
(8) A patterned conductive laminate obtained by the method for producing a patterned conductive laminate according to (6) or (7).
(9) The conductive laminate according to (1), wherein the metal-based linear structure is a silver nanowire.
(10) The conductive laminate according to (1), wherein the inorganic particles have an average particle size of 500 nm or less.
(11) The patterned conductive laminate according to any one of (3), (4), (5), and (8) above, wherein an average void diameter of voids contained in the nonconductive region is 500 nm or less body.
(12) The conductive laminate as described in (1) above, wherein the inorganic particles are carbonates.
(13) A display using the conductive laminate according to (1) or the patterned conductive laminate according to any of (3), (4), (5), and (8).
(14) A touch panel using the display body according to (13).
(15) Electronic paper using the display according to (13).

  ADVANTAGE OF THE INVENTION According to this invention, the conductive laminated body from which the non-visibility of a pattern part becomes high after forming a pattern, and the patterned conductive laminated body from which the non-visibility of a pattern part is high can be provided.

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 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.

[Conductive laminate]
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 | surface of a base material, and you may have a conductive layer on both surfaces of a base material. 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. As the hard coat layer, 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. As 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.

[Base material]
Specific examples of the material for the base material in the conductive laminate of the present invention include transparent resin and glass. Examples of 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. For example, 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. As for the shape of the base material, it may be a film that can be wound up with a thickness of 250 μm or less, or a substrate with a thickness of more than 250 μm, as long as it is within the range of the total light transmittance described later. From the viewpoint of cost, productivity, handleability, etc., a resin film of 250 μm or less is preferable, more preferably 190 μm or less, still more preferably 150 μm or less, and particularly preferably 100 μm or less. When using 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. Among 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. In addition, 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.

[Metallic linear structure]
Examples of the metal-based linear structure in the present invention include fibrous conductors, nanowires, acicular conductors such as whiskers and nanorods. The term “fibrous” means that the aspect ratio = the length of the major axis (the length of the metallic linear structure) / the length of the minor axis (the diameter of the metallic linear structure) is greater than 10. 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. It is a structure. Note that the metal-based linear structure may exist in the form of an aggregate in addition to the case where it exists alone. As for the aggregate, for example, 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. As an example of 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. Including noble metals (eg, gold, platinum, silver, palladium, rhodium, iridium, ruthenium, osmium, etc.) and 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, Examples of 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.

[Network structure]
In the present invention, 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. At this time, 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. Here, 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.

[matrix]
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.

  Examples of the matrix component 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, 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, Nyltrimethoxysilane, vinyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3, 3, 3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, 2-hydroxyethyltrimethoxysilane, 2-hydroxyethyltriethoxysilane, 2-hydroxypropyltrimethoxysilane, 2-hydroxypropyl Triethoxysilane, 3-hydroxypropyltrimethoxysilane, 3-hydroxypropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropioxy Triethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meta ) Acrylicoxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, vinyltriacetoxysilane and the like.

  Examples of the organic polymer include a thermosetting resin and a photocurable resin. For example, 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. Among these organic polymers, a polymer having a structure in which a compound having three or more carbon-carbon double bond groups is polymerized is preferable. Such an organic polymer is made from a composition containing at least one selected from the group consisting of a monomer, an oligomer, and a polymer having three or more functional groups containing a carbon-carbon double bond, and a carbon-carbon double bond. It can obtain by carrying out a polymerization reaction using as a reaction point.

Examples of the functional group including 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. Amide group, arylidene group, allylidine group, vinyl ether group, or those in which hydrogen bonded to carbon constituting the carbon-carbon double bond of these groups is substituted with halogen atoms such as fluorine and chlorine (for example, vinyl fluoride group Vinylidene fluoride group, vinyl chloride group, vinylidene chloride group, etc.). In addition to these, 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 ) — (R1, R2 is 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. Ethoxytrimethacrylate, pentaerythritol ethoxytetraacrylate, pentaerythritol ethoxytetramethacrylate, dipentaerythritol triacrylate, dipentaerythritol trimethacrylate, dipentaerythritol tetraacrylate, dipentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol penta Tacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, trimethylolpropane ethoxytriacrylate, trimethylolpropane ethoxytrimethacrylate, ditrimethylolpropane triacrylate, ditrimethylolpropane triacrylate Methacrylate, ditrimethylolpropane tetraacrylate, ditrimethylolpropane tetramethacrylate, glycerin propoxytriacrylate, glycerin propoxytrimethacrylate, and compounds having a cyclic skeleton such as cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring in the molecule (for example, , Triacrylate Trimethacrylate, tetraacrylate, tetramethacrylate, pentaacrylate, pentamethacrylate, hexaacrylate, hexamethacrylate, etc.) and compounds obtained by modifying some of these compounds (for example, 2-hydroxypropanoic acid modified with 2-hydroxypropanoic acid etc.) Pentaerythritol triacrylate, 2-hydroxypropanoic acid-modified pentaerythritol trimethacrylate, 2-hydroxypropanoic acid-modified pentaerythritol tetraacrylate, 2-hydroxypropanoic acid-modified pentaerythritol tetramethacrylate, silicone triacrylate having a silicone skeleton, silicone Trimethacrylate, silicone tetraacrylate, silicone tetramethacrylate, silicone pen Acrylate, silicone pentamethacrylate, silicone hexaacrylate, silicone hexamethacrylate, etc.) and compounds having other skeletons together with vinyl groups and / or vinylidene groups in the skeleton (for example, urethane triacrylate, urethane trimethacrylate, urethane having a urethane skeleton) Tetraacrylate, urethane tetramethacrylate, urethane pentaacrylate, urethane pentamethacrylate, urethane hexaacrylate, urethane hexamethacrylate, polyether triacrylate with ether skeleton, polyether trimethacrylate, polyether tetraacrylate, polyether tetramethacrylate, polyether penta Acrylate, polyether pentamethacrylate, polyester Terhexaacrylate, polyether hexamethacrylate, epoxy triacrylate with epoxy-derived skeleton, epoxy trimethacrylate, epoxy tetraacrylate, epoxy tetramethacrylate, epoxy pentaacrylate, epoxy pentamethacrylate, epoxy hexaacrylate, epoxy hexamethacrylate, ester skeleton Polyester triacrylate, polyester trimethacrylate, polyester tetraacrylate, polyester tetramethacrylate, polyester pentaacrylate, polyester pentamethacrylate, polyester hexamethacrylate, etc.). In consideration of application, required characteristics, productivity, etc., a composition 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 Although the composition formed from can be used, it is not specifically limited to these. Among these compounds, a compound having 4 or more carbon-carbon double bond groups that contribute to the polymerization reaction, that is, a tetrafunctional or more functional compound can be more preferably used. Examples of the tetrafunctional or higher functional compound include the tetrafunctional tetraacrylate, tetramethacrylate, pentafunctional pentaacrylate, pentamethacrylate, hexafunctional hexaacrylate, hexamethacrylate, and the like.

  These compounds are commercially available, for example, Kyoeisha Chemical Co., Ltd. light acrylate series, light ester series, epoxy ester series, urethane acrylate AH series, urethane acrylate AT series, urethane acrylate UA series, Daicel -EBECRYL series manufactured by Cytec Co., Ltd., PETIA, TMPTA, TMPEOTA, OTA 480, DPHA, PETA-K, full cure series manufactured by Soken Chemical Co., Ltd., "LIODURAS" manufactured by Toyo Ink Co., Ltd. (Registered trademark) series, Folceed series manufactured by China Paint Co., Ltd., EXP series manufactured by Matsui Kagaku Co., Ltd., EBECRYL 1360 manufactured by Daicel Cytec Co., Ltd., X manufactured by Shin-Etsu Chemical Co., Ltd. 12-2456 Series, and the like.

[Inorganic particles]
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.

  In the present invention, various carbonates, inorganic compounds that can be dissolved by acid treatment, such as zinc oxide, tin oxide, and ITO can be used. Among them, 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. Here, 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. As a method for obtaining such data, for example, an image obtained by observing a cross section of a layer containing inorganic particles with a field emission scanning electron microscope (SEM) (JSM-6700-F manufactured by JEOL Ltd.) may be used. Good. In addition, 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. When the particles are in an aggregated state, 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.

[void]
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. 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. In order to obtain diffuse reflection light, 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]. At this time, 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.

  Next, a void generation method will be described. The void in the present invention is generated by dissolving or decomposing the aforementioned inorganic particles. Specifically, 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. And a method of generating voids. Among these methods, 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.

[Layer containing inorganic particles]
The layer containing inorganic particles in the present invention can be disposed at any position in the conductive laminate. For example, 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.

  Moreover, it can also be set as the layer containing an inorganic particle by disperse | distributing an inorganic particle in a matrix or the easily bonding layer of a base material.

  Above all, in order to express the effect that the pattern visibility of the conductive layer is improved at the same time as the patterning of the conductive layer when adopting the chemical etching method, and the layer containing inorganic particles from the viewpoint of manufacturing cost reduction by reducing the number of steps, It is desirable to dispose on the conductive layer side. In addition, as described in [Inorganic particles], 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. When 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. In addition, when 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. In addition, as an upper limit of layer thickness, 1 micrometer or less is preferable from viewpoints, such as a softness | flexibility of a conductive laminated body, and handleability. From the viewpoint of this layer thickness, 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.

  As the 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 substrate and the conductive layer.

  That is, when the conductive layer is provided only on one side of the base material, it is preferable to have a layer containing inorganic particles between the base material and the conductive layer.

  On the other hand, 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.

  As 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. Examples of 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. Among these, 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. Moreover, after apply | coating to the unstretched film the easily bonding layer solution which disperse | distributed the inorganic particle when forming a base film, it can be extended | stretched and the easily bonding layer containing an inorganic particle can also be formed on a base film. .

[Patterned conductive laminate]
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.

  Next, a method for manufacturing the patterned conductive layer will be described. 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. As 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. Among these coating methods, 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.

  Next, a method for forming a non-conductive region will be described. Formation of 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. In the present invention, 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. 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. Preferably it is 90% or more.

  In the present invention, 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.

In the conductive laminate of the present invention, the surface resistance value on the conductive layer side is preferably 1 × 10 ¹ Ω / □ or more and 1 × 10 ⁴ Ω / □ or less, more preferably 1 × 10 ¹ Ω / □. □ or more and 1.5 × 10 ³ Ω / □ or less. By being in this range, it can be preferably used as a conductive laminate for a touch panel. That is, if it is 1 × 10 ¹ Ω / □ or more, the power consumption can be reduced, and if it is 1 × 10 ⁴ Ω / □ or less, the influence of errors in the coordinate reading of the touch panel can be reduced.

  Various 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. Examples of 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.

  Further, 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. As the 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. In the present invention, an acrylic pressure-sensitive adhesive, a silicone-based pressure-sensitive adhesive, a urethane-based pressure-sensitive adhesive, and the like can be used. In particular, 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. Among them, 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. A network structure having contact points (any or more) 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.

[Layer with voids]
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.

  That is, when it has a patterned conductive layer 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.

  On the other hand, when it has a patterned conductive layer on both surfaces of a base material, (i) even if it has a layer where a void exists between any patterned conductive layer formed on both surfaces of the base material and the base material Alternatively, (ii) 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.

  Further, as described in the section of [Void], the void of the present invention is generated by dissolution or decomposition of inorganic particles. 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. When 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. In addition, if 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 exists is preferable if it has a sufficient layer thickness 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 | flexibility of a patterned conductive laminated body, handling property.

  As the 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.

Hereinafter, the present invention will be specifically described based on examples. However, the present invention is not limited to the following examples.
[Evaluation method]
First, an evaluation method in each example and comparative example will be described.

(1) Form of conductive component Using an insulation resistance meter (manufactured by Sanwa Denki Keiki Co., Ltd., DG6), a probe is applied to each surface of the sample, and the conductive surface of the sample is specified from the presence or absence of energization.

  Next, the surface of each of the conductive region (A) and the 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 image contrast were appropriately adjusted, and observation was performed at each magnification.

  If observation by the above method is difficult, then a color 3D laser microscope (VK-9700 / 9710 manufactured by Keyence Corporation), an observation application (VK-H1V1 manufactured by Keyence Corporation), and a shape analysis application (Keyence Corporation) Using VK-H1A1), the attached 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 (CF IC EPI Plan Apo 150X manufactured by Nikon Corporation) was used to observe the same position on the conductive side at each magnification, and image analysis was performed from the image data.

(2) Identification of conductive component and inorganic particles The conductive layer was peeled from the sample and dissolved in a solvent to be dissolved. If necessary, apply general chromatography such as silica gel column chromatography, gel permeation chromatography, liquid high-speed chromatography, etc., and separate and purify each into a single substance for the following qualitative analysis .

  Thereafter, 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.

  Analysis methods were combined with the following analysis methods, and those that could 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, various 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.) X-ray diffraction (XRD), neutron diffraction (ND), low-energy electron diffraction (LEED), fast reflection electron diffraction (RHEED), atomic absorption spectrometry (AAS), ultraviolet photoelectron spectroscopy (UPS), Auger electron spectroscopy (AES), X-ray photoelectron spectroscopy (XPS), fluorescent X-ray elemental analysis (XRF), inductively coupled plasma emission spectroscopy (ICP-AES), electron microanalysis (EPMA), charged particles Excitation X-ray spectroscopy (PIXE), low energy ion scattering spectroscopy (RBS or LEIS), medium energy ion scattering spectroscopy (MEIS), high energy ion scattering spectroscopy (ISS or HEIS), gel permeation chromatography (GPC) , Transmission electron microscope-energy dispersive X-ray spectroscopic analysis (TEM-EDX), scanning electron microscope-energy dispersive X-ray spectroscopic analysis (SEM-EDX), gas chromatography (GC) and other elemental analysis.

(3) Surface resistance value R ₀
The surface resistance value on the conductive layer side of the conductive laminate was measured at a central portion of a 100 mm × 50 mm sample by an eddy current method using a non-contact type resistivity meter (NC-10 manufactured by Napson Co., Ltd.). An average value was calculated for three samples, and this was defined as a surface resistance value R ₀ [Ω / □]. When the surface resistance value was not obtained exceeding the detection limit, it was then measured by the following method.

Using a high resistivity meter (Hiresta-UP MCP-HT450 manufactured by Mitsubishi Chemical Corporation), 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 [Ω / □].

(4) Total light transmittance, haze A transparent adhesive on the PET film side of a 188 μm 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), using a turbidimeter (cloudiness meter) NDH2000 (Nippon Denshoku Industries Co., Ltd.) based on JIS K7361-1 (1997), conductive laminate 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.

(5) Diffuse reflected light The PET film side of a 188 μm thick optical PET film in which a hard coat layer (Forseed 423C manufactured by China Paint Co., Ltd.) is formed on one side of the conductive layer side of the sample is transparent adhesive (Nitto Denko Corporation) It was bonded together with LUCIACS CS9621T manufactured by Co., Ltd., and the reflected light on the conductive layer side was measured using a spectrocolorimeter CM-2600d (manufactured by Konica Minolta Sensing Co., Ltd.). The L ^* value of the L ^* a ^* b ^* color system in the SCE method was adopted as an index of diffuse reflection light. The measurement was performed in both the conductive region and the non-conductive region, and the ΔL ^* value, which is the difference between the L ^* values, was obtained.

(6) Evaluation of non-visibility of pattern When the ΔL ^* value in the above diffuse reflection measurement was 0.7 or less, it was judged that the non-visibility of the pattern was good. Further, 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 ΔL ^* ₀ value. This ΔL ^* 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 ΔL ^* ₀ value increases. Here, when ΔL ^* −ΔL ^* ₀ ≦ −0.3 with an equivalent surface resistance value, it is determined that the non-visibility of the pattern has improved, and when ΔL ^* −ΔL ^* ₀ > −0.3 The non-visibility of the pattern was not improved and was regarded as defective. An equivalent surface resistance value is an equivalent surface resistance value within a range of a certain value ± 15Ω / □.

(7) Measurement of ΔL ^* ₀ value Four types of conductivity with surface resistance values of 140.1Ω / □, 150.5Ω / □, 162.0Ω / □, and 51.0Ω / □ without any inorganic particles in any layer A laminate was prepared. The ΔL ^* of the patterned conductive laminate obtained by patterning these was 1.93, 1.96, 2.02, and 3.27, and the respective values were ΔL ^* _{0 in} terms of the surface resistance value. . The conductive laminate and the patterned conductive laminate at this time were obtained by the same method as Comparative Examples 1 and 2 described later.

(8) Wet heat durability test A sample cut out to 100 mm x 50 mm was put into a thermo-hygrostat (PR-3SP manufactured by Tabai Espec Co., Ltd.) operated at a temperature and humidity condition 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.
(Surface resistance value of the sample after the test / Surface resistance value of the sample before the test) × 100 (%) (formula)
[material]
<Base material>
A 125 μm-thick polyethylene terephthalate film (“Lumirror” (registered trademark) U48 manufactured by Toray Industries, Inc.) was used.

<Metallic linear structure>
Metal-based linear structure "silver nanowire"
Silver nanowire (short axis: 50 to 100 nm, long axis: 20 to 40 μm)
<Matrix and undercoat>
(1) Acrylic composition A
An acrylic composition containing a compound having three or more carbon-carbon double bond groups contributing to the polymerization reaction as an acryloyl group (Furucure HC-6, manufactured by Soken Chemical Co., Ltd., solid content concentration 51% by mass). The cured product has a crosslinked structure.

(2) Photopolymerization initiator A
-Photopolymerization initiator having a maximum absorption wavelength of 300 nm (Ciba IRGACURE (registered trademark) 907 manufactured by Ciba Japan Co., Ltd.).

(3) Photopolymerization initiator B
-Photopolymerization initiator having a maximum absorption wavelength of 320 nm (Ciba IRGACURE (registered trademark) 369, manufactured by Ciba Japan Co., Ltd.).

<Easily adhesive layer composition>
(1) 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.

Next, 53.5 g of acrylic composition A, 1.29 g of photopolymerization initiator A, 1.29 g of photopolymerization initiator B, 886.9 g of ethyl acetate, and 60.0 g of dispersion of inorganic particles A were mixed and stirred, and the undercoat The material was prepared. This undercoat material was applied to a substrate using a slit die coat equipped with a shim made of sus (shim thickness: 50 μm), dried at 120 ° C. for 2 minutes, and then cured by irradiation with ultraviolet rays of 80 mJ / cm ^2. An undercoat layer having a thickness of 600 nm was formed.

  Next, 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 μm), and dried at 120 ° C. for 2 minutes to form a conductive component. .

  Subsequently, 26.7 g of acrylic composition A, 0.16 g of photopolymerization initiator A, 0.16 g of photopolymerization initiator B, and 972.0 g of ethyl acetate were mixed and stirred to prepare a matrix composition.

The prepared matrix composition was applied using a slit die coat with shim (shim thickness 50 μm) 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.

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 154.8Ω / □.

  Next, three sheets of the obtained conductive laminate were cut out to a size of 50 mm × 100 mm and prepared as a sample for confirming the invisibility of the pattern.

  Next, 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.

  Next, a dispersion of inorganic particles A was obtained using the same materials and methods as in Example 1.

Next, 53.5 g of acrylic composition A, 0.32 g of photopolymerization initiator A, 0.32 g of photopolymerization initiator B, 886.9 g of ethyl acetate, and 60.0 g of dispersion of inorganic particles A were mixed and stirred to form a matrix composition. A product was prepared.
The prepared matrix composition was applied using a slit die coat with shim (shim thickness 50 μm) 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. Irradiation and curing were performed to form a conductive layer having a matrix portion thickness of 600 nm to obtain a conductive laminate.

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. Further, the surface resistance value R ₀ of this conductive laminate was 156.0Ω / □.

  Subsequently, 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.

Next, 53.5 g of acrylic composition A, 1.29 g of photopolymerization initiator A, 1.29 g of photopolymerization initiator B, 886.9 g of ethyl acetate, and 60.0 g of dispersion of inorganic particles A were mixed, stirred, and hard coated. The material was prepared. This hard coat material was applied to a substrate using a slit die coat equipped with a shim made of sus (shim thickness 50 μm), dried at 120 ° C. for 2 minutes, and then cured by irradiating with 80 mJ / cm ^{2 of} ultraviolet rays to obtain a thickness. A hard coat layer having a thickness of 600 nm was formed.

  Next, a conductive component and a matrix were formed on the opposite surface on which the hard coat layer was formed in the same manner as in Example 1 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 167.3Ω / □.

  Subsequently, 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. In addition, since 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 μm 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. Further, the surface resistance value R ₀ of this conductive laminate was 50.3Ω / □.

  Subsequently, 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 153.5Ω / □.

  Subsequently, 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)
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 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 20% by mass with respect to the undercoat material. The average particle diameter of the inorganic particles was 154 nm. Further, the surface resistance value R ₀ of this conductive laminate was 57.5Ω / □.
Subsequently, 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 156 nm and the pattern non-visibility has not reached a good level, but the inorganic particles and / or voids have the same surface resistance value. It was improved as compared with the patterned conductive laminate containing no.

(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 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. Further, the surface resistance value R ₀ of this conductive laminate was 144.2 Ω / □.

  Subsequently, 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 μm 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 50.8Ω / □.

  Subsequently, 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 subjected to vibration dispersion for 2 hours using 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. Further, the surface resistance value R ₀ of this conductive laminate was 163.3Ω / □.

  Subsequently, 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 C10.0 g, water 54.0 g, isopropyl alcohol 36.0 g, 200.0 g of zirconia beads 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 Corporation) 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.

  Next, 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. Furthermore, the dispersion of the coating liquid A, the coating liquid B, and the inorganic particles C of the easy-adhesion layer composition in solid mass ratio, the dispersion of the coating liquid A / the coating liquid B / the inorganic particles C = 25/75 / 8.4. 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.

  Subsequently, 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 μm, and the thickness of the easy adhesion layer was 350 nm.

Next, a conductive component and a matrix were laminated on the substrate in the same manner as in Example 4 to obtain a conductive laminate. 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. Further, the surface resistance value R ₀ of this conductive laminate was 53.0Ω / □.

  Subsequently, 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.

(Comparative 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 152.7Ω / □.

  Subsequently, 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 μm 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 53.8Ω / □.

  Subsequently, 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 applications such as touch panels, liquid crystal displays, and electronic papers because of their good pattern non-visibility.

1: 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

Claims (15)

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 further including inorganic particles in any layer of the conductive laminate. A conductive laminate characterized by that. The conductive laminate according to claim 1, further comprising a layer containing inorganic particles between the substrate and the conductive layer. A patterned conductive laminate having a patterned conductive layer on at least one side of a substrate, the patterned conductive layer comprising a conductive region in which a metal-based linear structure having a network structure is present, and a metal-based having a network structure A patterned conductive laminate having a non-conductive region in which no linear structure is present, and further having a void in any layer of the laminated structure of the non-conductive region. 4. The patterned conductive laminate according to claim 3, further comprising a layer having voids between the substrate and the patterned conductive layer. 5. The patterned conductive laminate according to claim 4, wherein more voids are present in the non-conductive region than in the conductive region. It is a manufacturing method of the patterned electrically conductive laminated body in any one of Claim 3, 4, 5, Comprising: A void is formed by melt | dissolving the inorganic particle of the electrically conductive laminated body of Claim 1 or 2 by a chemical | medical solution process. A method for producing a patterned conductive laminate, comprising: The pattern according to claim 6, wherein the void is formed by dissolving the inorganic particles in the chemical treatment, and at the same time, the metal-based linear structure having the network structure is also removed to form a non-conductive region. Method for producing a conductive laminate. A patterned conductive laminate obtained by the method for producing a patterned conductive laminate according to claim 6. The conductive laminate according to claim 1, wherein the metal-based linear structure is a silver nanowire. The conductive laminate according to claim 1, wherein the average particle diameter of the inorganic particles is 500 nm or less. The patterned conductive laminate according to any one of claims 3, 4, 5, and 8, wherein an average void diameter of voids contained in the non-conductive region is 500 nm or less. The conductive laminate according to claim 1, wherein the inorganic particles are carbonates. A display body using the conductive laminate according to claim 1 or the patterned conductive laminate according to any of claims 3, 4, 5, and 8. A touch panel using the display body according to claim 13. Electronic paper using the display according to claim 13.

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